Photo- or thermosetting resin composition and cured resin thereof, and semiconductor package and printed circuit board using the cured resin

Abstract

To provide a light- or heat-curable resin composition that gives a cured resin suitable for a permanent insulation film, the cured resin being less prone to cracks or breaks and having reliable adhesion to a substrate and high chemical resistance while ensuring the alkali developer resistance, moisture resistance durability, and heat thermostability of a pattern part.SOLUTION: A light- or heat-curable resin composition contains, based on 100 pts.mass of an unsaturated group-containing alkali-soluble resin (A) of formula (1), an alkylene oxide-modified product of at least one acrylate selected from methacrylates or oligomers thereof (B) of 10-100 pts.mass and an epoxy group-containing compound (C) of 0.1-50 pts.mass, and a photopolymerization initiator and / or photosensitizer (D) of 0.01-10 pts.mass.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photo- or thermosetting resin composition suitable as an insulating material for semiconductor packages and printed circuit boards, a cured resin product thereof, and a semiconductor package and a printed circuit board using the cured resin product as an insulating layer. [Background technology]

[0002] In recent years, as electronic devices have become smaller, printed wiring has become increasingly multilayered to enable higher integration of electronic elements, and the so-called build-up method, in which insulating and conductor layers are alternately formed and laminated, has become widely adopted. High reliability is also required for the resin insulating materials used in this method. Furthermore, wiring boards often have a protective insulating layer on their surface to protect the surface and the chips mounted on them.

[0003] However, in this multilayer wiring board, the thermal expansion coefficient of the resin insulating material is significantly different from that of the active components such as semiconductor elements, passive components such as capacitive elements and resistors, and also from that of the substrate such as a glass epoxy resin formed by impregnating an aluminum oxide sintered body or a glass cloth woven with glass fiber with epoxy resin, or a silicon wafer. The difference in the thermal expansion coefficient between the two components causes large thermal stress, which in turn causes cracks and breaks in the semiconductor elements, capacitive elements, wiring conductors, etc., preventing the semiconductor elements, etc. from operating normally. This is a drawback.

[0004] The applicants of the present application have already reported on a resin insulating material for such printed wiring board applications in Patent Document 1. According to Patent Document 1, by using an acrylate in which an ethylenically unsaturated carboxylic acid is modified with alkylene oxide to impart flexibility to a cured film, a cured film that excels in reliability tests such as thermal reliability tests is obtained, and this is used as a method for preventing the occurrence of fine cracks that can cause dielectric breakdown, for example.

[0005] However, because alkylene oxides, especially ethylene oxide, are highly hydrophilic, when the number of modifications is high, the patterned area is easily peeled off by alkaline developer, and moisture absorption can cause a significant drop in electrical resistance or short circuits in humidity resistance tests such as highly accelerated life tests (HAST) and high-temperature, high-humidity bias tests (THB). Furthermore, sufficient adhesion reliability was required to prevent peeling from the substrate.

[0006] Furthermore, if the number of modifications is large, the crosslink density decreases, which lowers the glass transition point, and there is a concern that the heat resistance to the thermal history during processes including reflow will deteriorate and sufficient reliability of adhesion to the substrate will not be obtained. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 4558178 Summary of the Invention [Problem to be solved by the invention]

[0008] In response to these problems associated with conventional resin compositions and their cured resins, the present inventors have conducted extensive research into methods for suppressing the occurrence of cracks and breakage while ensuring alkaline developer resistance, moisture resistance reliability, and heat resistance in patterned areas in resin insulating materials used in semiconductors and substrates. As a result, they have found that by using an acrylic monomer or acrylic oligomer with a specific structure, i.e., an acrylate having two or more double bonds and 2 to 15 alkylene oxide modifications, and further using a silane coupling agent having a functional group reactive with other resin components in the composition, it is possible to achieve both film formability, moisture resistance reliability, and heat resistance, as well as suppression of cracks and breakage in thermal tests in a resin insulating material formed from the resin composition, and further to ensure sufficient adhesion reliability to the substrate, chemical resistance, etc., and have completed the present invention.

[0009] Therefore, an object of the present invention is to solve the above problems and to provide a photo- or thermosetting resin composition suitable for a permanent insulating film, which is excellent in suppressing the occurrence of cracks and breakages while ensuring alkaline developer resistance, moisture resistance reliability, and heat resistance of the pattern portion, and further has excellent adhesion reliability to the substrate, chemical resistance, etc. [Means for solving the problem]

[0010] That is, the gist of the present invention is as follows. [1] A composition comprising, relative to 100 parts by mass of an unsaturated group-containing alkali-soluble resin (A) represented by the following formula (1), 10 to 100 parts by mass of an alkylene oxide-modified product (B) of at least one acrylate selected from (meth)acrylates or oligomers thereof, 0.1 to 50 parts by mass of a compound (C) containing an epoxy group, and 0.01 to 10 parts by mass of a photopolymerization initiator and / or a photosensitizer (D), and further comprising 0.1 to 10% by mass of a silane coupling agent (E) having a reactive functional group, based on the solid content: The component (B) is a photo- or thermosetting resin composition having two or more carbon-carbon double bonds and 2 to 15 alkylene oxide modifications. [ka] [In formula (1), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms 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. Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number from 0 to 3. Each G is independently a (meth)acrylic acid residue, a substituent represented by general formula (2), or a substituent represented by general formula (3). Y is a tetravalent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by general formula (4), and at least one Z is a substituent represented by general formula (4). n has an average value of 1 to 20.] [ka] [ka] [In formulas (2) and (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is 0 to 10.] [ka] [In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.] [2] The photo- or thermosetting resin composition according to [1], characterized in that, in the solid content, the (A) component is 30 to 80 mass %, the (B) component is 10 to 40 mass %, the (C) component is 5 to 50 mass %, the (D) component is 1 to 5 mass %, and the (E) component is 0.5 to 5 mass %. [3] The photo- or thermosetting resin composition according to [1] or [2], wherein the component (A) has a weight average molecular weight of 1,000 to 100,000 and an acid value of 50 to 200 mgKOH / g. [4] The photo- or thermosetting resin composition according to any one of [1] to [3], further comprising at least one unsaturated compound (F) selected from other monomers and oligomers in an amount of 100 parts by mass or less per 100 parts by mass of component A. [5] A cured resin obtained by curing the photo- or thermosetting resin composition according to any one of [1] to [4], characterized in that the cured resin has a glass transition temperature of 100°C or higher and a tensile elongation of 5% or higher. [6] A semiconductor package using the cured resin according to [5] as at least one insulating layer. [7] A printed circuit board comprising at least one insulating layer made of the cured resin according to [5]. [Effects of the Invention]

[0011] The heat- or photo-curable resin composition of the present invention provides a cured resin product suitable for a permanent insulating film that is excellent in suppressing the occurrence of cracks and breakages while ensuring alkaline developer resistance, moisture resistance reliability, and heat resistance in the patterned portion, and that also has excellent adhesion reliability to the substrate, chemical resistance, etc. Furthermore, by selecting the resin used, the composition can have heat resistance and fine processability due to its high glass transition temperature, and is particularly useful as a resin composition for forming peripheral materials for electronic components such as semiconductor elements using a build-up method, for example, insulating layers in multilayer printed wiring boards, WLCSPs, etc. DETAILED DESCRIPTION OF THE INVENTION

[0012] As described above, the photo- or thermosetting resin composition of the present invention contains (A) an unsaturated group-containing alkali-soluble resin represented by the following formula (1), (B) an alkylene oxide-modified product of at least one acrylate selected from (meth)acrylates or their oligomers, (C) an epoxy group-containing compound, (D) a photopolymerization initiator and / or photosensitizer, and (E) a silane coupling agent having a reactive functional group reactive with functional groups of other resin components in the composition. The present invention will be explained below by describing these components in detail.

[0013] <Component (A)> First, we will explain component (A). Component (A) of the present invention is a polymerizable, unsaturated-group-containing, alkali-soluble resin represented by general formula (1), and as described below, is obtained by reacting a reaction product of an epoxy compound (a-1) having two glycidyl ether groups with (meth)acrylic acid or a derivative thereof, with a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof (b), and a tetracarboxylic acid or an acid dianhydride thereof (c). Note that "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and refers to either or both of these. The same applies to (meth)acrylates.

[0014] The unsaturated group-containing alkali-soluble resin is characterized in that it uses, as a raw material epoxy compound, a compound in which Ar in general formula (1) is an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may contain several oxyalkylene groups in one molecule.

[0015] Preferred examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a divalent naphthyl group and a phenylene group in which some of the hydrogen atoms may be substituted with an alkyl group, etc. Here, it is preferred that both of the two Ars bonded to the fluorene group in general formula (1) are naphthyl groups (having a bisnaphtholfluorene skeleton) or both are phenylene groups (having a bisphenolfluorene skeleton).

[0016] [ka]

[0017] [In formula (1), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms 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. Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number from 0 to 3, the average value of l in one molecule is also a number from 0 to 3, and the average value of l in the composition is also a number from 0 to 3. Each G is independently a (meth)acrylic acid residue, a substituent represented by general formula (2), or a substituent represented by general formula (3). Y is a tetravalent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by general formula (4), and at least one Z is a substituent represented by general formula (4). n has an average value of 1 to 20.]

[0018] [ka]

[0019] [ka]

[0020] [In formulas (2) and (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is 0 to 10.]

[0021] [ka]

[0022] [In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.]

[0023] A method for producing the alkali-soluble resin containing a polymerizable unsaturated group represented by general formula (1) will be described in detail below.

[0024] First, an epoxy compound (a-1) (hereinafter simply referred to as "epoxy compound (a-1)") having a fluorene skeleton and represented by general formula (5), which may have several oxyalkylene groups in one molecule, is reacted with either (meth)acrylic acid, a (meth)acrylic acid derivative represented by general formula (6), or a (meth)acrylic acid derivative represented by general formula (7), or a mixture thereof, to obtain an epoxy (meth)acrylate.

[0025] [ka]

[0026] [In formula (5), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the bonded hydrogen atoms 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. Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and each 1 is independently a number from 0 to 3.]

[0027] [ka]

[0028] [ka]

[0029] [In formulas (6) and (7), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.]

[0030] The reaction of the epoxy compound (a-1) with (meth)acrylic acid and / or the (meth)acrylic acid derivative can be carried out by a known method. For example, Japanese Patent Application Laid-Open No. 4-355450 discloses 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. In the present invention, the compound obtained by the reaction is a diol (d) containing a polymerizable unsaturated group represented by formula (8) (hereinafter, also simply referred to as "diol (d) represented by general formula (8)").

[0031] [ka]

[0032] (In formula (8), Ar, R1, and l are the same as in formula (5). Each G is independently a (meth)acrylic acid residue, a substituent represented by general formula (2) or a substituent represented by general formula (3).)

[0033] In the synthesis of the diol (d) represented by the general formula (8) and the subsequent reaction with a polycarboxylic acid or anhydride thereof to produce the alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (1), the reaction is usually carried out in a solvent using a catalyst as needed.

[0034] Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate; and ketone-based solvents such as cyclohexanone and diisobutyl ketone. The reaction conditions, such as the solvent and catalyst used, are not particularly limited, but it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

[0035] Furthermore, it is preferable to use a catalyst in the reaction between an epoxy group and a carboxyl group or a hydroxyl group, and JP-A-9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0036] Next, the diol (d) represented by general formula (8) obtained by the reaction of the epoxy compound (a-1) with the (meth)acrylic acid derivative is reacted with a dicarboxylic acid or tricarboxylic acid or its acid anhydride (b), and a tetracarboxylic acid or its acid dianhydride (c), to obtain an alkali-soluble resin represented by the general formula (1) having a carboxy group and a polymerizable unsaturated group in one molecule.

[0037] Next, G constituting the alkali-soluble resin represented by general formula (1) will be described. As described above, G is each independently a (meth)acrylic acid residue (i.e., a residue in which the terminal OH group has been removed from (meth)acrylic acid), a substituent represented by general formula (2), or a substituent represented by general formula (3). Among these, the substituent represented by general formula (2) or general formula (3) derived from the (meth)acrylic acid derivative represented by general formula (6) or general formula (7) is as follows:

[0038] General formulas (2), (3), (6), and (7) each have a polymerizable unsaturated group and at least one ester bond, where R2 is a hydrogen atom or a methyl group, and R3 is a divalent alkylene or alkylarylene group having 2 to 10 carbon atoms.

[0039] The alkylene group may be either straight-chain or branched, and includes ethylene, ethylidene, vinylene, vinylidene, propylene, trimethylene, propenylene, isopropylidene, and tetramethylene groups.

[0040] Furthermore, the alkylarylene group may be an unsubstituted arylene group as long as it is within the range of the number of carbon atoms, such as o-, m-, or p-phenylene, toluylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, or pentylphenylene.

[0041] R4 in the general formulae (2), (3), (6) and (7) is a saturated or unsaturated aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms.

[0042] The saturated and unsaturated aliphatic hydrocarbon groups may be either straight-chain or branched, and include ethylene, ethylidene, vinylene, vinylidene, propylene, trimethylene, propenylene, isopropylidene, and tetramethylene groups.

[0043] The aromatic hydrocarbon group may be unsubstituted as long as it is within the range of the number of carbon atoms, and may be, for example, o-, m-, or p-phenylene, toluylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, or pentylphenylene, and may be substituted with 2 to 4 substituents as long as the number of carbon atoms does not exceed the range. The aliphatic hydrocarbon group may be interrupted by an unsaturated bond, an ether bond, or an ester bond.

[0044] Furthermore, when synthesizing the alkali-soluble resin represented by general formula (1), each p is independently a number from 0 to 10, but the average value of p in the resin is preferably a number from 0 to 5, and more preferably a number from 0 to 2. When the average value of p is within the above range, the distribution of the flexible structure, alkylene oxide, can be prevented from becoming too wide, and sufficient curability can be imparted to the cured film without reducing the resin performance.

[0045] The acid component used to synthesize the alkali-soluble resin represented by general formula (1) is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule represented by general formula (8). It is necessary to use a dicarboxylic acid or tricarboxylic acid or its monoanhydride (b) in combination with a tetracarboxylic acid or its dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated or unsaturated hydrocarbon group. Furthermore, these carboxylic acid residues may contain bonds containing heteroatoms such as -O-, -S-, or carbonyl groups.

[0046] Examples of the dicarboxylic acid or tricarboxylic acid or their acid monoanhydrides (b) include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their acid monoanhydrides.

[0047] Examples of the acid monoanhydrides of the chain hydrocarbon dicarboxylic or tricarboxylic acids include acid monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0048] Examples of the acid monoanhydrides of the alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like, as well as acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0049] Examples of the acid monoanhydrides of the aromatic hydrocarbon dicarboxylic or tricarboxylic acids include acid monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, etc., and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0050] Among the above dicarboxylic acid or tricarboxylic acid monoanhydrides, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred.

[0051] In addition, in the case of dicarboxylic acids or tricarboxylic acids, it is preferable to use their acid monoanhydrides. The acid monoanhydrides of the dicarboxylic acids or tricarboxylic acids described above may be used alone or in combination of two or more thereof.

[0052] Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, and acid dianhydrides thereof.

[0053] Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0054] Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids into which a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0055] Examples of aromatic hydrocarbon tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0056] Alternatively, bis(trimellitic anhydride) aryl esters can be used. Bis(trimellitic anhydride) aryl esters are a group of compounds produced, for example, by the method described in International Publication No. 2010 / 074065, and are structurally dianhydrides formed by ester bonding between two hydroxyl groups of an aromatic diol (such as naphthalenediol, biphenol, or terphenyldiol) and the carboxyl groups of two molecules of trimellitic anhydride. These compounds are hereinafter referred to as bis(trimellitic anhydride) esters of aromatic diols.

[0057] Among the above tetracarboxylic acids or their acid dianhydrides, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are more preferred. Furthermore, among the above tetracarboxylic acids or their acid dianhydrides, it is preferred to use the acid dianhydrides. Furthermore, bis(trimellitic anhydride) esters of naphthalenediol can also be preferably used. The above tetracarboxylic acids or their acid dianhydrides, and bis(trimellitic anhydride) esters of aromatic diols can be used alone or in combination of two or more.

[0058] The reaction of the diol (d) represented by the general formula (8) with the acid components (b) and (c) is not particularly limited, and any known method can be used. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method in which an epoxy (meth)acrylate is reacted with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0059] Here, it is preferable to react the compound so that the terminals of the compound become carboxy groups, and so that the molar ratio of the epoxy (meth)acrylate (d), dicarboxylic acid or tricarboxylic acid or their acid monoanhydrides (b), and tetracarboxylic acid dianhydride (c) is (d):(b):(c)=1.0:0.01-1.0:0.2-1.0.

[0060] For example, when using acid monoanhydride (b) and acid dianhydride (c), the molar ratio of the amount of acid component [(b) / 2 + (c)] to the amount of diol (d) containing a polymerizable unsaturated group, [[(b) / 2 + (c)] / (d)]], is preferably 0.5 to 1.0. Here, when the molar ratio exceeds 0.5, the content of unreacted diol containing a polymerizable unsaturated group is not increased, thereby improving the stability of the alkali-soluble resin composition over time. On the other hand, when the molar ratio is 1.0 or less, the terminal of the alkali-soluble resin represented by formula (1) is not converted to an acid anhydride, thereby preventing an increase in the content of unreacted acid dianhydride, thereby improving the stability of the alkali-soluble resin composition over time. The molar ratios of components (b), (c), and (d) can be arbitrarily changed within the above-mentioned ranges in order to adjust the acid value and molecular weight of the alkali-soluble resin represented by formula (1).

[0061] The acid value of the alkali-soluble resin represented by general formula (1) is preferably in the range of 50 to 200 mgKOH / g, and more preferably 60 to 120 mgKOH / g. When the acid value is 50 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 prevented from becoming too rapid, thereby suppressing peeling development. The acid value can be determined, for example, by titration with a 1 / 10N aqueous KOH solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0062] The weight-average molecular weight (Mw) of the alkali-soluble resin represented by general formula (1), measured by gel permeation chromatography (GPC) (e.g., HLC-8220GPC, manufactured by Tosoh Corporation) in terms of polystyrene, is usually 1,000 to 100,000, and more preferably 3,000 to 40,000. When the weight-average molecular weight is 1,000 or more, it is possible to suppress a decrease in the adhesion of the pattern during alkaline development. Furthermore, when the weight-average molecular weight (Mw) is 100,000 or less, it is easy to adjust the solution viscosity of the photo- or thermosetting resin composition to a level suitable for application, and alkaline development does not require excessive time.

[0063] Next, a photo- or thermosetting resin composition using the alkali-soluble resin represented by general formula (1) of the present invention will be described.

[0064] In the photo- or thermosetting resin composition of the present invention, the content of component (A) is preferably 30 to 80 mass % based on the total mass of the solid content. Furthermore, with respect to components (B) to (E) described below, the proportions of components (B), (C), and (E) per 100 parts by mass of component (A) are 10 to 100 parts by mass of component (B), 0.1 to 50 parts by mass of component (C), and 0.1 to 20 parts by mass of component (E). In addition, the proportion of component (A) in the solid content is 30 to 80 mass%, the proportion of component (B) is 10 to 40 mass%, the proportion of component (C) is 5 to 50 mass%, the proportion of component (D) is 1 to 5 mass%, and the proportion of component (E) is 0.1 to 10 mass%, preferably 0.5 to 5 mass%.

[0065] <(B) component> Next, the component (B) will be described. The component (B) is an alkylene oxide-modified (adduct) product of at least one acrylate selected from (meth)acrylates or their oligomers. The component (B) may be an alkylene oxide-modified product of a (meth)acrylate, an alkylene oxide-modified product of an oligomer of such a (meth)acrylate, or a mixture of these.

[0066] Here, the number of carbon-carbon double bonds contained in the structure of this component (B) is set to two or more because it forms a crosslinked structure with component (A) and allows the mechanical properties of the photo- or thermosetting product to be designed within the desired range. There is no upper limit to the number of carbon-carbon double bonds, but it is preferably 10 or less, more preferably 8 or less. Furthermore, because it is necessary to ensure crack resistance, heat resistance, chemical resistance, etc., the number of bonds modified with alkylene oxide needs to be 2 to 15. The lower limit is preferably 4 or more, more preferably 8 or more, and even more preferably 10 or more. On the other hand, the upper limit is preferably 12 or less.

[0067] Examples of (meth)acrylates that can be used as raw materials for this alkylene oxide modified product (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, hexanediol (meth)acrylate, long-chain aliphatic di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, propylene di(meth)acrylate, glycerol (meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, dicyclopentaerythritol di(meth)acrylate, and methyl methyl acrylate. Examples of bifunctional compounds include methyl methyl di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene di(meth)acrylate, triglycerol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, methoxylated cyclohexyl di(meth)acrylate, acrylated isocyanurate, bis(acryloxyneopentyl glycol) adipate, bisphenol A di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, bisphenol S di(meth)acrylate, butanediol di(meth)acrylate, phthalic acid di(meth)acrylate, phosphoric acid di(meth)acrylate, and zinc di(meth)acrylate.

[0068] Furthermore, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, phosphate tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, tris(methacryloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Examples of the compound include tri- or higher functional compounds such as tetra(meth)acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, urethane tri(meth)acrylate, ester tri(meth)acrylate, urethane hexa(meth)acrylate, and ester hexa(meth)acrylate.

[0069] Furthermore, examples of the (meth)acrylate oligomer that serves as the raw material for the alkylene oxide modified product (B) of the present invention include the above-mentioned (meth)acrylate oligomers.

[0070] The composition of the present invention may contain alkylene oxide modified monofunctional compounds as long as it does not contradict the object of the present invention. Examples of monofunctional compounds that can be used as raw materials for such modified compounds include those having a hydroxyl group, such as (meth)hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, butanediol mono(meth)acrylate, and chlorohydroxypropyl (meth)acrylate; and those having a hydroxyl group, such as allyl (meth)acrylate, butoxyethyl (meth)acrylate, and butanediol mono(meth)acrylate. Triethylene glycol (meth)acrylate, t-butylaminoethyl (meth)acrylate, caprolactone (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, cyanoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylamino (meth)acrylate, ethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate acrylate, octyl (meth)acrylate, stearyl (meth)acrylate, succinic acid (meth)acrylate, methacryloxypropyltrimethoxysilane, methoxyethyl (meth)acrylate, cyclodecatriene (meth)acrylate, glycerol (meth)acrylate, glycidyl (meth)acrylate, isocyanatoethyl (meth)acrylate, decafluoroheptyl (meth)acrylate, octafluoropentyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, trifluoroe aliphatic (meth)acrylates such as ethyl (meth)acrylate and dibromopropyl (meth)acrylate; alicyclic modified (meth)acrylates such as cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and morpholine (meth)acrylate; and cycloaliphatic modified (meth)acrylates such as phenoxyethyl (meth)acrylate and phenoxyhydroxypropyl (meth)acrylate.Examples of the acrylate include aromatic (meth)acrylates such as nonylphenoxy polypropylene glycol (meth)acrylate, phenyl (meth)acrylate, phthalic acid (meth)acrylate, and benzyl (meth)acrylate; phosphorus-containing (meth)acrylates such as phenoxylated phosphate (meth)acrylate, phosphate (meth)acrylate, butoxylated phosphate (meth)acrylate, and octoxylated phosphate (meth)acrylate; and water-soluble (meth)acrylates such as sodium sulfonate (meth)acrylate.

[0071] The bifunctional, trifunctional or higher functional compounds or oligomers thereof that are the raw materials for component (B) can be used singly or in combination of two or more. The monofunctional compounds that are the raw materials can also be used singly or in combination of two or more.

[0072] <(C) component> Next, we will explain component (C), which is a compound containing an epoxy group. Component (C) is used to improve adhesion and alkali resistance. Examples of component (C) used for this purpose include epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, and alicyclic epoxy resins, as well as compounds containing at least one epoxy group such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate. While an epoxy curing agent can be used with component (C), the presence of a compound containing a carboxyl group, such as component (A), does not necessarily require the use of a curing agent.

[0073] <(F) Component> The heat- and photo-curable resin composition of the present invention may contain, as a resin or resin-forming component (hereinafter, both components are collectively referred to as resin components), at least one other unsaturated compound (F) (hereinafter also referred to as component (F)) selected from other photopolymerizable monomers and oligomers in addition to the above-mentioned components (A), (B), and (C) (including a curing agent, if used). Examples of such component (F) include various vinyl monomers having one or more unsaturated groups, such as (meth)acrylic acid, (meth)acrylate, and styrene, as well as various oligomers, such as hydrocarbon resins. In particular, when the resin composition of the present invention is required to have excellent photocurability in addition to alkali solubility, i.e., high sensitivity, it is preferable to incorporate an oligomer or monomer having two or more polymerizable double bonds (bifunctional), more preferably three or more (trifunctional), per molecule.

[0074] Regarding the blending ratio of the above oligomers and monomers, when excellent photocuring properties are required, generally, if the blending amount of tri- or higher functional polyfunctional acrylates, etc. is small, photocuring does not proceed sufficiently, and the exposed parts may be eluted, while if the blending amount is too large, even the unexposed parts may not be developable, and there is a risk of losing tack-free properties depending on the degree of polymerization and the structure of the acid anhydride.

[0075] The amount of such component (F) is preferably 0 to 100 parts by mass per 100 parts by mass of component (A) in the resin component.

[0076] <(D) component> Furthermore, the component (D) used in the present invention as a photopolymerization initiator and / or photosensitizer includes those used as photopolymerization initiators and / or photosensitizers for the unsaturated compounds used as components (A), (B), and (F). Examples of component (D) used for this purpose include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and ptert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzoin ethers such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenone; and the like. Biimidazole compounds such as 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole; halomethyldiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole;2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) )-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and other halomethyl-s-triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), O-Acyloxime compounds such as 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, and 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate; benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropyl sulfur compounds such as thioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and pentaerythritol tetrakis(3-mercaptopropionate);Examples include tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, and triethylamine. These photopolymerization initiators and / or sensitizers (D) can be used alone or in combination of two or more. Note that component (D) is not necessarily required for thermally polymerizable resin compositions, but is important when forming a pattern by exposure to light, development, etc.;

[0077] The total amount of the photopolymerization initiator and / or photosensitizer used is 0.01 to 10 parts by mass per 100 parts by mass of component (A), but preferably 1 to 5 parts by mass. If the amount exceeds 10 parts by mass, the light absorption rate will be high, and there is a risk that light will not penetrate to the bottom. Furthermore, the amount of the photopolymerization initiator and / or photosensitizer added is preferably 0.01 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the total of components (A), (B), and (F).

[0078] <(E) component> The photo- or thermosetting resin composition of the present invention also requires, as component (E), a silane coupling agent having a functional group (reactive functional group) reactive with functional groups of other resin components, etc., in the composition. The incorporation of a silane coupling agent having such a reactive functional group can ensure adhesion at the portion where the photo- or thermosetting resin composition of the present invention comes into direct contact with an inorganic substrate, such as a glass substrate or a silicon wafer. This is advantageous in that it can improve the reliability of semiconductor packages and printed circuit boards. Examples of silane coupling agents having a reactive functional group reactive with functional groups of resin components, etc., include epoxy-based silane coupling agents having an epoxy group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; vinylacetoxysilane; vinyltrieth ... silane coupling agents having a double bond, such as trimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, and p-styryltrimethoxysilane;3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, N-(p-vinylbenzyl)-N-(trimethoxysilylpropyl) Amine-based silane coupling agents having an amino group, such as ethylenediamine, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-triethoxysilyl-N-propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; ureido-based silane coupling agents having a ureido group, such as 3-ureidopropyltriethoxysilane; isocyanate-based silane coupling agents having an isocyanate group, such as 3-isocyanatepropyltriethoxysilane; [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methyl]propyltrimethoxysilane, Examples of suitable silane coupling agents include oxetanyl-based silane coupling agents having an oxetanyl group, such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; mercapto-based silane coupling agents having a mercapto group, such as 3-trimethoxysilylpropylsuccinic anhydride; acid anhydride-based silane coupling agents having an acid anhydride, such as 3-trimethoxysilylpropylsuccinic anhydride; imide-based silane coupling agents having an imide group, such as Nt-butyl-3-(3-trimethoxysilylpropyl)succinimide; and oligomeric coupling agents having an alkoxy group and an organic functional group, such as a silicone oligomer. Two or more of these may be used. Silane coupling agents having a functional group reactive with a carboxy group, such as an epoxy group, are more preferred. Specific examples include 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane. Two or more of these may be used.

[0079] It may also be used in combination with other silane coupling agents. Examples of other silane coupling agents include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. Two or more of these may be contained.

[0080] The amount of component (E) is 0.1 to 10% by mass, preferably 0.5 to 5% by mass, of the solid content. If the amount of component (E) exceeds 10% by mass, patterning properties and storage stability deteriorate. If it is less than 0.1% by mass, adhesion to the substrate cannot be ensured.

[0081] In addition to the above essential components, the photo- or thermosetting resin composition of the present invention may contain additives such as epoxy resin curing accelerators, polymerization inhibitors, plasticizers, leveling agents, and antifoaming agents, as needed. Examples of epoxy resin curing accelerators include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic compounds.

[0082] Furthermore, the viscosity of the photo- or thermosetting resin composition of the present invention can be adjusted by blending a solvent, if necessary. The solvent must dissolve the matrix resin component and not react with the resin and additives of the matrix resin component, and is not particularly limited as long as it satisfies these conditions. When the total amount of the solid content, including the components that become solid after photo- or thermal polymerization, and the solvent is taken as 100%, the amount of the solvent can be 30 to 95% by mass so that the solution viscosity of the photosensitive resin composition solution falls within a predetermined range.

[0083] The glass transition temperature of the cured resin obtained by curing the photo- or thermosetting resin composition of the present invention is preferably 100°C or higher, more preferably 150°C or higher, from the viewpoint of heat resistance. Furthermore, from the viewpoint of reliability, the tensile elongation is preferably 5% or higher, more preferably 10% or higher. Increasing the number of alkylene oxide modifications is considered preferable to improve tensile elongation, but on the other hand, heat resistance tends to decrease relatively. Therefore, it is preferable to adjust the formulation so as to balance tensile elongation and heat resistance. Furthermore, the cured resin preferably has a small amount of warpage measured by the method described below, and more preferably has an interfacial stress of 30 MPa or less, which is calculated by the formula described below and which correlates with the amount of warpage. Furthermore, it is preferable that the cured resin product ensures adhesion reliability with the substrate, and for this purpose, it is preferable to adjust the formulation of the composition. That is, in the reliability evaluation described below, it is preferable that the reliability is 95% or more, more preferably 98% or more, and most preferably 100%. In addition, in the evaluation of adhesive strength (shear strength) described below, it is preferable that the adhesive strength is 10 MPa or more, more preferably 15 MPa or more. In the evaluation of adhesive strength described below, it is preferable that the adhesive strength is 100 kg / cm or more. 2 It is preferable that the strain is equal to or greater than 150 kg / cm. 2 In addition to these evaluations, it is preferable that the evaluations of chemical resistance and solder heat resistance, which will be described later, be at least "△" or higher, more preferably "◯" or higher, and even more preferably "◎".

[0084] Furthermore, the photo- or thermosetting resin composition of the present invention can also be used in the form of a dry film. Since the photo- or thermosetting resin composition of the present invention can be exposed and developed, it can also be used as an insulating material, adhesive, etc., that require the formation of fine patterns. It is particularly useful as an insulating layer material for wiring boards. The cured product provides a highly reliable cured film, making it useful as an insulating film for printed wiring boards and semiconductor packages, such as a solder resist layer, a plating resist layer, an etching resist layer, a buffer coat layer, a rewiring layer, and an interlayer insulating layer. In this application, the term "semiconductor package" refers not only to flip-chip packages and wafer-level packages, but also to those that include a semiconductor chip and are mounted on a printed circuit board, such as a flip-chip package stacked on an interposer. It may also be used to prepare top coats for paints and inks, hard coats for plastics, and rust-preventive films for metals.

[0085] When the photo- or thermosetting resin composition of the present invention is used as an insulating layer material for a wiring board, the method for forming a conductor layer on the surface of the cured resin layer is not particularly limited. For example, the resin composition is applied to a substrate by spin coating, curtain coating, etc., followed by drying, exposure, and development to form a circuit, followed by thermal curing. The surface of the cured resin layer can be planarized with a buff, if necessary, and then a known dry plating process can be applied. A known electrolytic copper plating process can then be applied to form a conductor layer. Furthermore, a multilayer wiring board can be produced by repeatedly applying a resin composition to the conductor layer, forming a circuit, thermal curing, and then forming a conductor layer. Furthermore, if the conductor layer is exposed, the resin composition can also be used as a protective film. The printed wiring board of the present invention can be produced in this manner. In this case, it is necessary to use the photo- or thermosetting resin composition of the present invention as the resin composition forming at least one cured resin layer. When the cured resin layer is multilayered, using the photo- or thermosetting resin composition of the present invention for most of the cured resin layers can result in a more reliable multilayer printed wiring board. The photo- or thermosetting resin composition of the present invention can also be used as a protective film on the surface of a wiring board, or as an insulating resin layer for protecting chips and the like mounted on a wiring board. [Example]

[0086] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0087] The abbreviations used in the synthesis examples are as follows. BPFE: Bisphenol fluorene type epoxy resin [epoxy resin with general formula (5) where Ar is a benzene ring and l is 0, epoxy equivalent weight 256] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride TPP: Triphenylphosphine AA: Acrylic acid

[0088] [Synthesis Example 1: Preparation of Unsaturated Group-Containing Alkali-Soluble Resin (A)] A 250 mL four-neck flask equipped with a reflux condenser was charged with BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g), and PGMEA (40.00 g), and the mixture was stirred at 100 to 105°C for 12 hours to obtain a reaction product. Then, PGMEA (25.00 g) was added to adjust the solid content to 50% by mass.

[0089] Next, BPDA (14.37 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the resulting reaction product and stirred at 115 to 120°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin (A). The solids concentration of the resulting resin solution was 57.0 mass%, the acid value (solids equivalent) was 96 mg KOH / g, and the Mw by GPC analysis was 3600.

[0090] (alkali-soluble resin) (A): Unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 1 (solid content concentration: 57.0% by mass)

[0091] (Alkylene oxide modified product) (B)-1: Trimethylolpropane triacrylate ethylene oxide 6 mole adduct (Aronix M-360, manufactured by Toagosei Co., Ltd.) (B)-2: 4-mol ethylene oxide adduct of bisphenol A diacrylate (Light Acrylate BP-4EA, manufactured by Kyoeisha Chemical Co., Ltd.) (B)-3: 10 moles of ethylene oxide adduct of bisphenol A diacrylate (Light Acrylate BP-10EA, manufactured by Kyoeisha Chemical Co., Ltd.) (B)-4: Dipentaerythritol hexaacrylate with 12 moles of ethylene oxide (KAYARAD DPEA-12, manufactured by Nippon Kayaku Co., Ltd.) (B)-5: Trimethylolpropane triacrylate ethylene oxide 15 mole adduct (T-70EA, manufactured by Toho Chemical Industry Co., Ltd.) (B)-6: Trimethylolpropane triacrylate ethylene oxide 45 mole adduct (T-200EA, manufactured by Toho Chemical Industry Co., Ltd.)

[0092] (epoxy compounds) (C): Tetramethylbiphenyl type epoxy resin (YX4000, manufactured by Mitsubishi Chemical Corporation)

[0093] (Photoinitiator / Photosensitizer) (D-1): 2,2-dimethoxy-2-phenylacetophenone (OMNIRAD651 manufactured by IGM Resins B.V.) (D-2): Michler's ketone

[0094] (Silane coupling agent with reactive functional groups that are reactive with functional groups of resin components, etc.) (E)-1:3-Glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.) (E)-2: 3-Methacryloxypropylmethyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) (E)-3: 3-Ureidopropyltriethoxysilane (KBE-585, Shin-Etsu Chemical Co., Ltd.) (E)-4: 3-Isocyanatepropyltriethoxysilane (KBE-9007, Shin-Etsu Chemical Co., Ltd.)

[0095] (unsaturated compound) (F)-1: Trimethylolpropane triacrylate (SR351S, manufactured by Sartomer Corporation) (F)-2: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA (acrylic equivalent: 96 to 115), manufactured by Nippon Kayaku Co., Ltd.)

[0096] (Other coupling agents) (G): Methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0097] (solvent) (H): Propylene glycol monomethyl ether acetate (PGMEA)

[0098] Table 1 shows the blending ratio of each component in the photo- or heat-curable resin composition. The blending amounts of components A to E in the table are listed as the amount of solids, including components that become solids after photo- or heat-curing.

[0099] [Table 1]

[0100] [evaluation] The following evaluations were carried out using the cured films (coating films) obtained by curing each of the compositions of Examples 1 to 17 and Comparative Examples 1 to 5. The results are shown in Table 2.

[0101] [Resolution] The photo- or thermosetting resin compositions shown in Table 1 were preliminarily heated with a low-pressure mercury lamp at a wavelength of 254 nm and an illuminance of 1000 mJ / cm. 2The coating was applied using a spin coater onto a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet light of 1000 W. The coating was then pre-baked on a hot plate at 110°C for 5 minutes to produce a cured film (coating film). Next, the illuminance of the 365 nm wavelength was 30 mW / cm 2 100mJ / cm through a quartz mask with a line / space of 10μm to 100μm. 2 The exposed film was then irradiated with ultraviolet light at 1 kgf / cm 2 to cause a photo-curing reaction in the photosensitive area. 2 After 20 seconds of development processing from the development time (break time = BT) when the pattern begins to appear, the shower pressure was increased to 5 kgf / cm 2 The exposed film was then spray washed with water to remove the unexposed portions of the exposed film, forming a line pattern on the glass substrate, which was then post-baked at 230°C for 30 minutes using a hot air dryer, and evaluated as the minimum line / space width (µm) that allows circuit formation with a film thickness of 10µm. It is preferable that the aspect ratio, calculated by dividing the film thickness by the minimum line / space width, be 1 or more.

[0102] [Linear expansion coefficient] (Creating a cured film) The photo- or thermosetting resin compositions shown in Table 1 were applied using a spin coater onto a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") to which an aluminum substrate with a release agent had been previously attached, so that the film thickness after heat curing would be 40 μm. The coating was then pre-baked on a hot plate at 110°C for 5 minutes to produce a cured film (coating). Next, the coating was heated at an illuminance of 30 mW / cm at a wavelength of 365 nm. 2 100mJ / cm with an ultra-high pressure mercury lamp 2 The exposed portions were then exposed to ultraviolet light at 230°C for 30 minutes (post-baking), and the cured films were peeled off from the aluminum substrates and processed to a size of 3 mm wide x 25 mm long to obtain cured films according to Examples 1 to 17 and Comparative Examples 1 to 5. (Evaluation of linear expansion coefficient) The cured film was subjected to thermomechanical analysis (TMA) (manufactured by Hitachi High-Tech Science Corporation) using a 3 mm wide cured film set so that the distance between chucks was 19 mm, and measurements were carried out in tensile mode at a temperature rise rate of 5°C / min over a measurement temperature range of 30°C to 270°C. The linear expansion coefficient was calculated using the thermal expansion amount between 30°C and 100°C using the following formula. α=ΔL / ((T2-T1)·L) ΔL: Amount of thermal expansion (μm) α: Linear expansion coefficient (ppm / K) T1: Temperature before change (℃) T2: Temperature after change (℃) L: Length in the direction for which you want to calculate thermal expansion (μm)

[0103] [Tensile modulus, tensile stress, tensile elongation] (Creating a cured film) Cured films prepared in the same manner as the cured films for evaluating the linear expansion coefficient were processed to a size of 10 mm wide x 150 mm long to obtain cured films according to Examples 1-17 and Comparative Examples 1-5. (Evaluation of tensile properties) Using an automatic film strength and elongation measuring device (AMF / RTA-100 manufactured by Orientec Co., Ltd.), a 10 mm wide cured film was set so that the distance between the chucks was 40 mm, and a tensile test was performed at a temperature of 23°C and an atmospheric condition of 55% RH (relative humidity) at a pulling speed of 5 mm / min. Ten samples were measured in the longitudinal direction of the film, and the tensile modulus, tensile stress, and tensile elongation were calculated using the following formulas. Tensile modulus (GPa) = Sum of the elastic moduli of the film measured in the longitudinal direction (for 10 samples) / 10 Tensile stress (MPa) = Sum of film stresses measured in the longitudinal direction (for 10 samples) / 10 Tensile elongation (%) = Sum of film elongations measured in the longitudinal direction (for 10 samples) / 10

[0104] [Glass transition temperature (Tg)] (Creating a cured film) Cured films prepared in the same manner as the cured films for evaluating the linear expansion coefficient were processed to a size of 5 mm wide x 18 mm long to obtain cured films according to Examples 1-17 and Comparative Examples 1-5. (Evaluation of glass transition temperature) The cured film was measured using a dynamic mechanical analyzer DMA (Rheogel-E4000, manufactured by UBM) with a 10 mm wide cured film set so that the distance between chucks was 15 mm. Measurements were performed in tension mode at a temperature rise rate of 4°C / min, with a sine wave frequency of 11 Hz, and a measurement temperature range of 30°C to 300°C. The glass transition point was determined as the peak temperature of the loss tangent tanδ calculated from the storage modulus E' and loss modulus E". tanδ=E” / E' E': storage modulus (Pa) E”: Loss modulus (Pa)

[0105] [Moisture resistance] (Creating test substrates for evaluating moisture resistance) The photo- or thermosetting resin compositions shown in Table 1 were applied to a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing would be 20 μm, and the substrate was prebaked on a hot plate at 110°C for 5 minutes to produce a cured film (coating film). Next, the substrate was heated at an illuminance of 30 mW / cm at a wavelength of 365 nm. 2 100mJ / cm with an ultra-high pressure mercury lamp 2 Then, the substrate was post-baked at 230°C for 30 minutes using a hot air dryer to obtain test substrates for evaluating moisture resistance according to Examples 1 to 17 and Comparative Examples 1 to 5. (Evaluation of moisture resistance) Using the test substrates prepared under the above conditions, a highly accelerated life tester (EMS-221MD manufactured by Espec Corporation) was used, and the substrates were left in the tester at 121°C, 85%, and 24 hours. After that, the appearance was checked and the moisture resistance was evaluated according to the following criteria. ⊚: The state of the cured film remains unchanged from the initial state, and no change is observed. ◯: The surface of the cured film was partially whitened, but almost no change was observed. △: Slight changes such as the occurrence of irregularities on the surface of the cured film were observed. ×: The entire cured film turned white, peeled off, or other obvious changes in appearance were observed.

[0106] [Reliability evaluation] (Creating test boards for reliability evaluation) A commercially available double-sided copper-clad FR-4 substrate (MCL-E-67 manufactured by Hitachi Chemical Co., Ltd., copper wiring thickness 18 μm) was used to create an evaluation pattern with 1350 × 4 dumbbell-shaped patterns, and the copper surface was roughened using the Neobrowne process of Ebara Densan Co., Ltd. to obtain an evaluation substrate. The photo- or thermosetting resin composition shown in Table 1 was applied to the prepared substrate using a spin coater so that the film thickness after heat curing would be 20 μm, and the substrate was pre-baked at 110°C for 5 minutes using a hot plate to produce a cured film (coating). Next, a 365 nm wavelength illuminance of 30 mW / cm was applied. 2 100mJ / cm with an ultra-high pressure mercury lamp 2 Then, the substrate was post-baked at 230° C. for 30 minutes using a hot air dryer to obtain test substrates for reliability evaluation according to Examples 1 to 5 and Comparative Examples 1 to 4. (Reliability assessment) The test substrates were subjected to a liquid immersion test of 250 cycles at temperatures between -65℃ and 125℃ (exposure time of 5 minutes each) using a thermal shock tester (TSB-1L manufactured by Espec Corporation), and the crack occurrence rate on each substrate was compared. The crack occurrence rate was calculated using the following formula to evaluate reliability. Reliability = [1-(number of cracks / total number of patterns)] x 100(%)

[0107] [Adhesive strength (shear strength)] (Creating test substrates for evaluating adhesive strength) The photo- or thermosetting resin compositions shown in Table 1 were applied to a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing would be 20 μm, and the substrate was prebaked on a hot plate at 110°C for 5 minutes to produce a cured film (coating film). Next, the substrate was heated at an illuminance of 30 mW / cm at a wavelength of 365 nm. 2 100mJ / cm with an ultra-high pressure mercury lamp 2 The exposed film was then irradiated with ultraviolet light at 1 kgf / cm 2 to cause a photo-curing reaction in the photosensitive area. 2 After 20 seconds of development processing from the development time (break time = BT) when the pattern begins to appear, the shower pressure was increased to 5 kgf / cm 2 The exposed film was then spray-washed with water to remove the unexposed portions, forming a 2 mm x 2 mm pattern on the glass substrate. A glass substrate cut to 2 mm x 2 mm was then placed on the pattern and temporarily bonded by heating on a hot plate at 100°C for 1 minute. This was followed by full curing (post-baking) at 230°C for 30 minutes using a thermal dryer, yielding test substrates for evaluating adhesive strength according to Examples 1 to 17 and Comparative Examples 1 to 5. (Evaluation of adhesive strength) Using the test substrate prepared under the above conditions, a die shear tester (manufactured by Arctec) was used to peel the substrate under a measurement load range of 100 kg, and the adhesive strength between the cured film and the interface between the glass substrate and the cured film was measured and evaluated according to the following criteria. ◎: Adhesive strength is 15 MPa or more. ○: Adhesion strength is 10 MPa or more and less than 15 MPa. △: Adhesion strength is 1 MPa or more and less than 10 MPa. ×: Adhesion strength cannot be measured.

[0108] [Adhesion strength] (Creating test substrates for evaluating adhesion strength) The photo- or thermosetting resin compositions shown in Table 1 were applied to a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing would be 20 μm, and the substrate was prebaked on a hot plate at 110°C for 5 minutes to produce a cured film (coating film). Next, the substrate was heated at an illuminance of 30 mW / cm at a wavelength of 365 nm. 2 100mJ / cm with an ultra-high pressure mercury lamp 2 The photosensitive portion was subjected to a photo-curing reaction by irradiating the film with ultraviolet light of 1000 W at 230°C for 30 minutes. The film was then post-baked at 230°C for 30 minutes using a hot air dryer. A 2.7 mm diameter stud pin with an epoxy adhesive was placed on the cured film, which was then dried in an oven set at a temperature of 80 to 120°C. The stud pin was then bonded to the cured film by heat curing at 150°C for 60 minutes using a hot air dryer, yielding test substrates for evaluating adhesion strength according to Examples 1 to 17 and Comparative Examples 1 to 5. (Evaluation of adhesion strength) Using the test substrate prepared under the above conditions, a stud-pull peel strength tester (Romulus, manufactured by Quad Group) was used to peel the glass substrate and the cured film at a force rate of 2 kg / sec, and the adhesion strength at the interface between the glass substrate and the cured film was measured and evaluated according to the following criteria. ◎: 150kg / cm 2 That's all. ○: 100kg / cm 2 More than 150kg / cm 2 less than. △: 50kg / cm 2 More than 100kg / cm 2 less than. ×:50kg / cm 2 below.

[0109] [warp] (Creating a test substrate for warpage evaluation) The photo- or thermosetting resin compositions shown in Table 1 were applied to a 100 mm x 100 mm x 60 μm aluminum substrate (hereinafter referred to as "aluminum substrate") using a spin coater so that the film thickness after heat curing would be 30 μm, and the coating was prebaked on a hot plate at 110°C for 5 minutes to produce a cured film (coating film). Next, the coating was heated at an illuminance of 30 mW / cm at a wavelength of 365 nm.2 500mJ / cm with an ultra-high pressure mercury lamp 2 Then, the substrate was post-baked at 230°C for 30 minutes using a hot air dryer to obtain test substrates for evaluating warpage according to Examples 1 to 17 and Comparative Examples 1 to 5. (Warpage evaluation) In the test substrate prepared under the above conditions, when viewed from the film thickness observation direction, a line connecting both edge portions on the cured film (coating film) side was used as a reference line, and the distance (perpendicular to the reference line) between this reference line and the most curved point on the aluminum substrate side was measured, and this distance was evaluated as the amount of warpage according to the following criteria. ◎: Warpage is less than 10 mm. ○: Warpage is 10 mm or more and less than 30 mm. △: Warpage is 30mm or more and less than 40mm. ×: Warpage is 40 mm or more, curling makes measurement impossible

[0110] [Interface Stress] (Calculation of interface stress) The interfacial stress when the film was applied to a silicon wafer as a substrate in the same manner as above was calculated from the measured values ​​of the tensile modulus, linear expansion coefficient, and glass transition point of the cured film using the following formula: σ = E×(α1A -α2B )×ΔT σ: Interfacial stress E: Tensile modulus of elasticity (Young's modulus) of the cured film α1A: Linear expansion coefficient of cured film α2B: Linear expansion coefficient of silicon wafer (4 ppm / K) ΔT: difference between Tg of cured film and room temperature (23°C) As mentioned above, in the cured resin product of the present invention, the interfacial stress is correlated with warpage, and it is more preferable that the interfacial stress is 30 MPa or less.

[0111] [Chemical resistance] (Creating test substrates for chemical resistance evaluation) The photo- or thermosetting resin compositions shown in Table 1 were applied to a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing would be 20 μm, and the substrate was prebaked on a hot plate at 110°C for 5 minutes to produce a cured film (coating film). Next, the substrate was heated at an illuminance of 30 mW / cm at a wavelength of 365 nm. 2 100mJ / cm with an ultra-high pressure mercury lamp 2 Then, the substrate was post-baked at 230°C for 30 minutes using a hot air dryer to obtain test substrates for evaluating moisture resistance according to Examples 1 to 17 and Comparative Examples 1 to 5. (Chemical resistance evaluation) The test substrate prepared under the above conditions was immersed in an acetone solution at room temperature for 30 minutes, and then the film thickness was measured, the remaining film rate was calculated, and the chemical resistance was evaluated according to the following criteria. Remaining film rate (%) = film thickness of the cured film after immersion ÷ film thickness of the cured film before immersion × 100 ⊚: The remaining rate of the cured film is 100%, and there is no change in appearance. ◯: The remaining rate of the cured film is 100%, but changes such as whitening in appearance are observed. △: The remaining film rate of the cured film is lower than 100%, and the film thickness is reduced. ×: The entire cured film peeled off, making measurement impossible.

[0112] [Solder heat resistance] (Creating test boards for evaluating solder heat resistance) A commercially available double-sided copper-clad FR-4 substrate (MCL-E-67 manufactured by Hitachi Chemical Co., Ltd., copper wiring thickness 18 μm) was used, and the copper surface was roughened using the Neobrowne process of Ebara Densan Co., Ltd. to obtain an evaluation substrate. On the prepared substrate, a photo- or thermosetting resin composition shown in Table 1 was applied using a spin coater to a 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") so that the film thickness after heat curing treatment would be 20 μm. The composition was then pre-baked on a hot plate at 110°C for 5 minutes to produce a cured film (coating). Next, a 365 nm wavelength illuminance of 30 mW / cm was applied. 2 100mJ / cm with an ultra-high pressure mercury lamp2 Then, the substrate was post-baked at 230°C for 30 minutes using a hot air dryer to obtain test substrates for evaluating moisture resistance according to Examples 1 to 17 and Comparative Examples 1 to 5. (Evaluation of solder heat resistance) The test substrate prepared under the above conditions was immersed in a solder bath at 260°C for 30 seconds in accordance with the test method of JIS C-6481, and a peeling test using cellophane tape was performed as one cycle.This was repeated 1 to 3 times, and the condition of the coating film was then visually observed and evaluated according to the following criteria. ◎: No abnormalities in the coating film even after 3 cycles. ○: After three cycles, slight changes were observed in the coating film. △: After repeating two cycles, changes were observed in the coating film. ×: After one cycle, changes were observed in the coating film.

[0113] [Table 2]

Claims

1. The composition contains, relative to 100 parts by mass of an unsaturated group-containing alkali-soluble resin (A) represented by the following formula (1), 10 to 100 parts by mass of an alkylene oxide-modified product (B) of at least one acrylate selected from (meth)acrylates or oligomers thereof, 0.1 to 50 parts by mass of a compound (C) containing an epoxy group, and 0.01 to 10 parts by mass of a photopolymerization initiator and / or a photosensitizer (D), and also contains 0.1 to 10% by mass of a silane coupling agent (E) having a reactive functional group, based on the solid content: Component (B) is a photo- or thermosetting resin composition characterized in that it has two or more carbon-carbon double bonds and 2 to 15 alkylene oxide modifications. 【Chemical 1】 [In formula (1), each Ar is independently a benzene ring. Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently the number 0. Each G is independently a (meth)acrylic acid residue. Each Y is a tetravalent biphenyltetracarboxylic acid residue. Each Z is independently a substituent represented by general formula (4). n is a number with an average value of 1 to 20.] 【Chemistry 2】 [In formula (4), W is a divalent tetrahydrophthalic acid residue, and m is 1.]

2. 2. The photo- or thermosetting resin composition according to claim 1, wherein the solid content is 30 to 80 mass % of the (A) component, 10 to 40 mass % of the (B) component, 5 to 12 mass % of the (C) component, 1 to 5 mass % of the (D) component, and 0.5 to 5 mass % of the (E) component.

3. 3. The photo- or thermosetting resin composition according to claim 1, wherein component (A) has a weight average molecular weight of 1,000 to 100,000 and an acid value of 50 to 200 mgKOH / g.

4. The photo- or thermosetting resin composition according to any one of claims 1 to 3, further comprising at least one unsaturated compound (F) selected from other monomers and oligomers in an amount of 100 parts by mass or less per 100 parts by mass of component A.

5. A resin cured product obtained by curing the photo- or thermosetting resin composition according to any one of claims 1 to 4, characterized in that the resin cured product has a glass transition temperature of 100°C or higher and a tensile elongation of 5% or higher.

6. A semiconductor package comprising at least one insulating layer made of the cured resin according to claim 5.

7. A printed circuit board comprising at least one insulating layer made of the cured resin according to claim 5.

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