Resin composition, cured product, and electronic component

Abstract

To provide a resin composition having high storage stability.SOLUTION: A resin composition contains a resin, a silane coupling agent having an alkoxysilyl group (A), and a compound having a hydrolyzable group (B). The relationship between Gibbs free energy change ΔGa when the alkoxysilyl group (A) reacts with water and Gibbs free energy change ΔGb when the hydrolyzable group (B) reacts with water satisfy ΔGa-ΔGb>0 kJ / mol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] An embodiment of the present invention relates to a resin composition, a cured product, and an electronic component. [Background technology]

[0002] In electronic components such as mounted circuit boards and hybrid integrated circuits (ICs), wiring is provided on a substrate made of glass epoxy, paper phenol, alumina ceramic, or the like, and various components such as a microcomputer, resistors, and capacitors are mounted on the substrate. In order to protect the wiring, electrodes, and the like from moisture, dust, and the like, a moisture-proof and insulating protective film is sometimes formed on the substrate. Photocurable resin compositions are widely used to form the protective film.

[0003] Patent Document 1 discloses a photocurable moisture-proof insulating coating material containing (A) a photocurable terminal acryloxypolybutadiene or terminal methacryloxypolybutadiene having a number average molecular weight of 300 to 10,000 and a hydrogenation rate of 90% or more, (B) a photopolymerization initiator, and (C) γ-methacryloxypropyltriethoxysilane. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-302946 Summary of the Invention [Problem to be solved by the invention]

[0005] In general, when a silane coupling agent is added to a photocurable resin composition, the adhesive strength between the protective film and the substrate tends to increase, and the insulating reliability tends to improve. However, after aging due to storage, a protective film formed using the photocurable resin composition has a reduced adhesive strength with the substrate, and sufficient insulating reliability may not be obtained.

[0006] Therefore, an object of one embodiment of the present invention is to provide a resin composition having excellent storage stability. Another embodiment of the present invention is to provide a cured product having excellent adhesiveness. Another embodiment of the present invention is to provide an electronic component having excellent reliability. [Means for solving the problem]

[0007] The present invention includes various embodiments. Examples of the embodiments are listed below. The present invention is not limited to the following embodiments.

[0008] (1) A composition comprising a resin, a silane coupling agent having an alkoxysilyl group (A), and a compound having a hydrolyzable group (B), a Gibbs free energy change ΔGa when the alkoxysilyl group (A) reacts with water and a Gibbs free energy change ΔGb when the hydrolyzable group (B) reacts with water satisfying ΔGa - ΔGb > 0 kJ / mol; Resin composition. (2) The resin composition according to (1) above, wherein the silane coupling agent further has a (meth)acryloyl group. (3) The resin composition according to (1) or (2) above, wherein the alkoxysilyl group includes a trimethoxysilyl group. (4) The resin composition according to any one of the above (1) to (3), wherein the hydrolyzable group (B) contains an isocyanate group. (5) The resin composition according to any one of the above (1) to (4), wherein the hydrolyzable group (B) contains an alkoxysilyl group. (6) The resin composition according to any one of (1) to (5) above, wherein the resin contains a resin having a polymerizable unsaturated group. (7) The resin composition according to any one of (1) to (6) above, further comprising a monomer having a polymerizable unsaturated group. (8) The resin composition according to (7) above, wherein the polymerizable unsaturated group contains a (meth)acryloyl group. (9) The resin composition according to any one of (1) to (8) above, which is a photocurable resin composition. (10) The resin composition according to any one of (1) to (9) above, which is a paint. (11) A cured product obtained by using the resin composition according to any one of (1) to (10) above. (12) An electronic component having the cured product described in (11) above. [Effects of the Invention]

[0009] According to an embodiment of the present invention, it is possible to provide a resin composition having excellent storage stability. Furthermore, according to another embodiment of the present invention, it is possible to provide a cured product having excellent adhesiveness. Furthermore, according to another embodiment of the present invention, it is possible to provide an electronic component having excellent reliability. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows the 29Si NMR spectrum of the resin composition after storage under specific conditions in the examples. [Figure 2] FIG. 2 is a schematic diagram of the ITO interdigital electrode substrate used in the examples. [Figure 3] FIG. 3 is a schematic diagram of a test piece used for evaluation in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0011] The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments.

[0012] In this specification, numerical ranges indicated using "to" include the numerical values before and after "to" as the minimum and maximum values, respectively. In the present specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. In addition, in the present specification, the upper or lower limit of a numerical range may be replaced with a value shown in the examples. In this specification, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In this specification, the term "film" includes cases where the film is formed over the entire area when the area where the film is present is observed, as well as cases where the film is formed over only a part of the area.

[0013] <Resin composition> According to an embodiment of the present invention, the resin composition contains a resin, a silane coupling agent having an alkoxysilyl group (A), and a compound having a hydrolyzable group (B). The resin composition may further contain an optional component such as a monomer having a polymerizable unsaturated group.

[0014] [resin] The resin composition contains a resin. Examples of the resin include thermosetting resins and thermoplastic resins, specifically acrylic resins, epoxy resins, acrylonitrile resins, bismaleimide resins, benzocyclobutene resins, phenolic resins, polyolefins, conjugated diene polymers, silicone resins, polyesters, polyurethanes, polyimides, polyamideimides, etc. The resin preferably contains hydrogenated polybutadiene or urethane oligomers, and more preferably contains hydrogenated polybutadiene.

[0015] The resin may have a polymerizable functional group. The polymerizable functional group may be a polymerizable unsaturated group, and examples thereof include groups having a carbon-carbon double bond, such as a vinyl group (ethenyl group), an ethynyl group, an allyl group, and a (meth)acryloyl group. The resin preferably has a (meth)acryloyl group. In this specification, "(meth)acrylic" is a general term for "acrylic" and "methacrylic," and "(meth)acrylate" is a general term for acrylate and methacrylate.

[0016] Examples of resins having a (meth)acryloyl group include hydrogenated polybutadiene having a (meth)acryloyl group, and urethane oligomers having a (meth)acryloyl group.

[0017] The hydrogenated polybutadiene having a (meth)acryloyl group (also referred to as "hydrogenated polybutadiene") has a (meth)acryloyl group at at least one end. Preferably, from the viewpoint of ease of introduction, the hydrogenated polybutadiene having a (meth)acryloyl group has a (meth)acryloyloxy group at at least one end. The hydrogenated polybutadiene having a (meth)acryloyl group can be used alone or in combination of two or more.

[0018] The number average molecular weight of the hydrogenated polybutadiene having (meth)acryloyl groups may be, for example, 900 to 10,000, 900 to 5,000, or 900 to 3,000, taking into consideration the curing rate, viscosity, flexibility of the cured product, etc. In the present disclosure, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a calibration curve prepared using standard polystyrene.

[0019] The (meth)acryloyl group may be introduced into the hydrogenated polybutadiene molecule via a urethane bond. Hydrogenated polybutadiene can be obtained, for example, by the following method. Hydroxy-terminated hydrogenated polybutadiene is reacted with a diisocyanate compound by a known method to obtain a reaction product having an isocyanate group at the terminal (a polymer having an isocyanate group at the terminal). The resulting reaction product is reacted with a (meth)acrylic acid ester having a hydroxyl group at the β-position by a known method to obtain hydrogenated polybutadiene. Examples of the diisocyanate compound include isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Examples of (meth)acrylic acid esters having a hydroxyl group at the β-position include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0020] Commercially available hydrogenated polybutadiene products include TE series / terminal acrylic group-introduced polybutadiene urethane bond type "TEAI-1000" manufactured by Nippon Soda Co., Ltd.

[0021] A urethane oligomer having a (meth)acryloyl group is a (meth)acrylate compound (excluding the aforementioned hydrogenated polybutadiene) that has a urethane bond in the molecule. When a bookbinding adhesive contains a urethane oligomer having a (meth)acryloyl group, it tends to be easier to control the mechanical properties of the cured product. The urethane oligomer having a (meth)acryloyl group can be used alone or in combination of two or more types.

[0022] The weight-average molecular weight of the urethane oligomer having a (meth)acryloyl group may be, for example, 800 to 10,000, 3,000 to 9,000, or 5,000 to 8,000, taking into consideration the curing rate, viscosity, flexibility of the cured product, etc. In the present disclosure, the weight-average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a calibration curve prepared using standard polystyrene.

[0023] Examples of the urethane oligomer include an ester-based urethane oligomer, an ether-based urethane oligomer, a carbonate-based urethane oligomer, etc. The urethane oligomer may be, for example, an addition reaction product of a (meth)acrylate having a hydroxyl group, a polyol, and a monomer containing a diisocyanate.

[0024] Commercially available urethane oligomers include, for example, "Art Resin UN-904" and "Art Resin UN-6060S" manufactured by Negami Chemical Industrial Co., Ltd.

[0025] The resin content may be, for example, 30% by mass or more, 40% by mass or more, 50% by mass or more, 65% by mass or more, or 80% by mass or more based on the mass of the resin composition from the viewpoints of viscosity characteristics, handleability, hardness after curing, etc. The resin content may be less than 100% by mass, 95% by mass or less, 90% by mass or less, 70% by mass or less, or 50% by mass or less from the viewpoints of storage stability, adhesiveness, etc.

[0026] When the resin composition contains a monomer having a polymerizable unsaturated group, which will be described later, the content of the resin may be, for example, 10 to 80 mass %, 20 to 70 mass %, 30 to 60 mass %, or 40 to 50 mass % based on the total mass of the resin and the monomer having a polymerizable unsaturated group, from the viewpoints of viscosity characteristics, handleability, hardness after curing, and the like.

[0027] [Silane coupling agent having an alkoxysilyl group (A)] The resin composition contains a silane coupling agent having an alkoxysilyl group (A) (sometimes referred to as silane coupling agent (a) in this specification). The alkoxysilyl group (A) may be a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group, preferably a dialkoxysilyl group or a trialkoxysilyl group, and more preferably a trialkoxysilyl group. The alkoxy group in the alkoxysilyl group (A) contains at least one selected from the group consisting of a methoxy group, an ethoxy group, and a propoxy group, and preferably contains a methoxy group. Specific examples of the alkoxysilyl group (A) include a trimethoxysilyl group and a triethoxysilyl group.

[0028] The silane coupling agent (a) may further have a reactive functional group. Examples of the reactive functional group include a (meth)acryloyl group, an epoxy group, an amino group, a vinyl group, a mercapto group, and an isocyanate group. The reactive functional group is preferably a group that can react with a resin to form a bond. The silane coupling agent (a) has, for example, a (meth)acryloyl group.

[0029] Specific examples of the silane coupling agent (a) include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, Examples of such silane include silane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

[0030] The content of the silane coupling agent (a) may be, for example, 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.2 mass% or more, or 1 mass% or more based on the mass of the resin composition from the viewpoint of adhesiveness. The content of the silane coupling agent (a) may be, for example, 15 mass% or less, 10 mass% or less, 5 mass% or less, 2 mass% or less, or 1 mass% or less based on the mass of the resin composition from the viewpoint of adhesiveness.

[0031] [Compounds having a hydrolyzable group (B)] The resin composition contains a compound having a hydrolyzable group (B) (sometimes referred to as compound (b) in this specification). Examples of the hydrolyzable group (B) include an alkoxysilyl group, an isocyanate group, an epoxy group, a urethane group (a group containing a urethane bond (-NH-C(O)-O-)), a carbonate group (a group containing a carbonate bond (-OC(O)-O-)), a carboxylic anhydride group (-C(O)-OC(O)-), an ether group (a group containing an ether bond), an imide group (a group containing an imide bond (-C(O)-N(-)-C(O)-)), an imidate group (a group containing an imidate ester bond (-C(NR)-O-)), a carboxylic amide group (a group containing an amide bond (-C(O)-NR-)), a carbonyl group (a group containing a carbonyl bond (-C(O)-)), and an ester group (a group containing an ester bond (-C(O)-O-)) (R is a monovalent or divalent group). The alkoxysilyl group may be a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group, preferably a dialkoxysilyl group, and more preferably a trialkoxysilyl group. The alkoxy group in the alkoxysilyl group includes at least one selected from the group consisting of a methoxy group, an ethoxy group, and a propoxy group, and preferably includes at least one selected from the group consisting of an ethoxy group and a propoxy group. Specific examples of the alkoxysilyl group include a triethoxysilyl group and a tripropoxysilyl group.

[0032] For example, compound (b) may have an alkoxysilyl group and a hydrolyzable group other than an alkoxysilyl group as the hydrolyzable group. Compound (b) having an alkoxysilyl group and a hydrolyzable group other than an alkoxysilyl group may be a compound that can function as a silane coupling agent. Examples of compound (b) having an alkoxysilyl group and a hydrolyzable group other than an alkoxysilyl group include a compound having an alkoxysilyl group and an isocyanate group, and a compound having an alkoxysilyl group and a carboxylic acid anhydride group. Specific examples include 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylethyldiethoxysilane, 3-isocyanatepropyltripropoxysilane, 3-isocyanatepropylpropyldipropoxysilane, 3-triethoxysilylpropylsuccinic anhydride, and 3-trippropoxysilylpropylsuccinic anhydride.

[0033] For example, compound (b) may have only hydrolyzable groups other than alkoxysilyl groups as hydrolyzable groups. Examples of compound (b) having only hydrolyzable groups other than alkoxysilyl groups include compounds having an isocyanate group, compounds having an isocyanate group and a (meth)acryloyloxy group, compounds having an epoxy group, compounds having a urethane group, compounds having a carbonate group, compounds having a carboxylic acid anhydride group, compounds having an ether group, compounds having an imide group, compounds having an imidate group, compounds having a carboxylic acid amide group, compounds having a carbonyl group, and compounds having an ester group. When compound (b) has only hydrolyzable groups other than alkoxysilyl groups as hydrolyzable groups, it is preferable that the hydrolyzable groups other than alkoxysilyl groups are groups that can react with at least one of the resin and the substrate to form a bond. Specific examples include 2-(2-(methacryloyloxyethyloxy)ethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, N-methylurethane, dimethyl carbonate, and the compounds listed as examples of ΔG described below.

[0034] The content of the compound (b) may be, for example, 0.01 mass % or more, 0.1 mass % or more, 1 mass % or more, or 5 mass % or more based on the mass of the resin composition from the viewpoint of storage stability. The content of the silane coupling agent (a) may be, for example, 20 mass % or less, 15 mass % or less, 10 mass % or less, 5 mass % or less, or 1 mass % or less based on the mass of the resin composition from the viewpoint of adhesiveness.

[0035] [ΔGa-ΔGb>0kJ / mol] In the resin composition, the Gibbs free energy change ΔGa when the alkoxysilyl group (A) of the silane coupling agent (a) reacts with water and the Gibbs free energy change ΔGb when the hydrolyzable group (B) of the compound (b) reacts with water satisfy the relationship ΔGa - ΔGb > 0 kJ / mol. Preferably, ΔGa - ΔGb > 20 kJ / mol, more preferably ΔGa - ΔGb > 50 kJ / mol. The alkoxysilyl group (A) is a dialkoxysilyl group ((R 1 O)(R 2 O)(H)Si-) or trialkoxysilyl group ((R 1 O)(R 2 O)(R 3 O)Si-) (R 1 ~R 3 are each independently an alkyl group.) R showing the largest ΔG n An alkoxysilyl group containing an O-Si bond (n is an integer of 1 to 3) may be used as the alkoxysilyl group (A). When the compound (b) has multiple hydrolyzable groups, the ΔGs of the multiple hydrolyzable groups are determined, the smallest ΔG among them is defined as ΔGb, and the hydrolyzable group showing this ΔGb is defined as the hydrolyzable group (B).

[0036] As ΔG of the hydrolyzable group, a value calculated using the following calculation software and conditions can be used. Calculation software: Gaussian09TM Revision E.01 Drawing software: Gauss view ver5.0.9 Condition: APFD / 6-31G(d,p) Temperature: 298.150 Kelvin. Pressure: 1.00000 Atm. Command: opt freq (structure optimization and frequency calculation)

[0037] The ΔG values calculated using the above calculation software and conditions for the hydrolyzable groups of several compounds are shown below. Ethoxysilyl group (3-isocyanatopropyltriethoxysilane) - 18 kJ / mol Isocyanate group (3-isocyanatepropyltriethoxysilane) -94kJ / mol Acryloyloxy group (3-acryloxypropyltrimethoxysilane) 206kJ / mol Methoxysilyl group (3-acryloxypropyltrimethoxysilane) -3 kJ / mol Urethane group (ethyl carbamate) - 47 kJ / mol Urethane group (N-methylcarbamate ethyl) -1 kJ / mol Carbonate group (dimethyl carbonate) - 75 kJ / mol Carbonate group (ethyl methyl carbonate) - 23 kJ / mol Ether group (ethyl methyl carbonate) -11 kJ / mol Ether group (diethyl ether) 14 kJ / mol Phthalimide group (N-methylphthalimide) 63kJ / mol Phthalimide group (phthalimide) 31kJ / mol Imidate group (ethyl N-hydroxyacetimidate) 2kJ / mol Imidate group (ethyl N-cyanoacetimidate) 8kJ / mol Carboxylic acid amide group (N-methylacetamide) 29 kJ / mol Carboxylic acid amide group (N,N-dimethylacetamide) 35kJ / mol Carboxylic anhydride group (acetic anhydride) - 31 kJ / mol Carboxylic acid anhydride group (succinic anhydride) 28kJ / mol Carbonyl group (acetaldehyde) -1 kJ / mol Carbonyl group (acetone) 35kJ / mol Isocyanate group (2-(acryloyloxy)ethyl isocyanate) -81kJ / mol Isocyanate group (1,1-(bisacryloyloxymethyl)ethyl isocyanate) - 77 kJ / mol Epoxy group (propylene oxide) - 49 kJ / mol Epoxy group (isobutylene oxide) - 45 kJ / mol Ester group (methyl acetate) 38kJ / mol Ester group (ethyl acetate) 37kJ / mol

[0038] Examples of the combination of the alkoxysilyl group (A) and the hydrolyzable group (B) include a combination of a methoxysilyl group (A) and an isocyanate group (B), and an ethoxysilyl group (A) and an isocyanate group (B).

[0039] The resin composition exhibits excellent storage stability by containing a silane coupling agent (a) and a compound (b) that satisfy ΔGa-ΔGb>0 kJ / mol. The reason for this is presumed to be as follows, for example. However, the present invention is not limited to the following. Generally, in silane coupling agents, the hydrolyzable silyl group is hydrolyzed to form silanols, which then bond with the substrate, thereby exhibiting adhesive strength. However, if the resin composition absorbs moisture during storage and the hydrolysis of the hydrolyzable silyl group progresses, the silanols react with each other and self-polymerize, resulting in the loss of silanols that contribute to adhesion to the substrate. In an embodiment of the present invention, a compound having a functional group more reactive with water than a hydrolyzable silyl group (i.e., a functional group with a small reaction Gibbs energy change ΔG) is added to the resin composition to suppress hydrolysis of the hydrolyzable silyl group during storage. That is, in an embodiment of the present invention, by containing a compound (b) having a functional group highly reactive with water in addition to a silane coupling agent (a) that contributes to improving adhesive strength, deterioration of the silane coupling agent (a) is prevented, and the resin composition exhibits excellent storage stability. Furthermore, the cured product formed using the resin composition containing the silane coupling agent (a) and the compound (b) exhibits excellent storage stability, and therefore has high adhesive strength even when the resin composition absorbs moisture during storage. Electronic components equipped with such a cured product as a protective film have excellent reliability.

[0040] The resin composition may be a composition containing one silane coupling agent (a) and one compound (b) that satisfy ΔGa-ΔGb>0 kJ / mol. For example, when the resin composition contains two or more silane coupling agents having alkoxysilyl groups, the alkoxysilyl group showing the largest ΔG can be designated as the alkoxysilyl group (A), and the silane coupling agent having the alkoxysilyl group (A) can be designated as the silane coupling agent (a). For example, when the resin composition contains two or more compounds having hydrolyzable groups, the hydrolyzable group showing the smallest ΔG can be designated as the hydrolyzable group (B), and the compound having the hydrolyzable group (B) can be designated as the compound (b).

[0041] Examples of combinations of silane coupling agent (a) and compound (b) include a silane coupling agent (a) having a trimethoxysilyl group and a compound (b) having an isocyanate group and an alkoxysilyl group, a silane coupling agent (a) having a trimethoxysilyl group and a compound (b) having an isocyanate group and a (meth)acryloyl group, etc. More specifically, 3-acryloxypropyltrimethoxysilane (silane coupling agent (a)) and 3-isocyanatepropyltriethoxysilane (compound (b)), 3-acryloxypropyltrimethoxysilane (silane coupling agent (a)) and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (compound (b)), etc.

[0042] [Monomers having polymerizable unsaturated groups] The resin composition may further contain a monomer having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include groups having a carbon-carbon double bond, such as a vinyl group (ethenyl group), an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamino group. The monomer having a polymerizable unsaturated group is a compound that does not fall under the category of silane coupling agent (a), i.e., a compound that does not have an alkoxysilyl group. The monomer having a polymerizable unsaturated group is a compound that does not have a hydrolyzable group (B) that satisfies ΔGa - ΔGb > 0 kJ / mol.

[0043] Examples of the monomer having a polymerizable unsaturated group include (meth)acrylic acid esters and (meth)acrylamides. The monomer having a polymerizable unsaturated group includes, for example, (meth)acrylic acid esters. The (meth)acrylic acid ester monomer having a polymerizable unsaturated group may be, for example, monofunctional to hexafunctional.

[0044] Examples of monofunctional (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, butoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and nonyl (meth)acrylate. , decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl acrylate, aliphatic (meth)acrylates such as hydroxybutyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, mono(2-(meth)acryloyloxyethyl)succinate, and reaction products of (meth)acrylic acid and glycidyl esters (for example, "Cardurer E-10" manufactured by Momentive Performance Materials); alicyclic (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, mono(2-(meth)acryloyloxyethyl)tetrahydrophthalate, and mono(2-(meth)acryloyloxyethyl)hexahydrophthalate.

[0045] Examples of the bifunctional (meth)acrylic acid ester monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 1,3- aliphatic (meth)acrylates such as butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, and ethoxylated 2-methyl-1,3-propanediol di(meth)acrylate;Cyclohexanedimethanol (meth)acrylate, ethoxylated cyclohexanedimethanol (meth)acrylate, propoxylated cyclohexanedimethanol (meth)acrylate, ethoxylated propoxylated cyclohexanedimethanol (meth)acrylate, tricyclodecane dimethanol (meth)acrylate, ethoxylated tricyclodecane dimethanol (meth)acrylate, propoxylated tricyclodecane dimethanol (meth)acrylate, ethoxylated propoxylated tricyclodecane dimethanol Examples of alicyclic (meth)acrylates include rodecanedimethanol (meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated hydrogenated bisphenol A di(meth)acrylate, ethoxylated propoxylated hydrogenated bisphenol A di(meth)acrylate, ethoxylated hydrogenated bisphenol F di(meth)acrylate, propoxylated hydrogenated bisphenol F di(meth)acrylate, and ethoxylated propoxylated hydrogenated bisphenol F di(meth)acrylate.

[0046] Examples of the trifunctional or higher (meth)acrylic acid ester monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, and propoxylated pentaerythritol tri(meth)acrylate. aliphatic (meth)acrylates such as pentaerythritol, ethoxylated propoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0047] The monomer having a polymerizable unsaturated group includes, for example, a monofunctional (meth)acrylic acid ester monomer, a difunctional (meth)acrylic acid ester monomer, or both of these. The monofunctional (meth)acrylic acid ester monomer may include an aliphatic (meth)acrylate, an alicyclic (meth)acrylate, or both of these.

[0048] When the resin composition contains a monomer having a polymerizable unsaturated group, the content of the monomer having a polymerizable unsaturated group may be, for example, 20 to 90 mass %, 30 to 80 mass %, 40 to 70 mass %, or 50 to 60 mass % based on the total mass of the resin and the monomer having a polymerizable unsaturated group, from the viewpoints of the curing speed, viscosity of the coating, moisture resistance and flexibility of the coating film, etc.

[0049] When the monomer having a polymerizable unsaturated group contains a monofunctional (meth)acrylic acid ester monomer and a difunctional (meth)acrylic acid ester monomer, the content of the difunctional (meth)acrylic acid ester monomer may be 1 to 35 mass%, 3 to 25 mass%, or 5 to 15 mass% based on the mass of the monomer having a polymerizable unsaturated group.

[0050] When the monomer having a polymerizable unsaturated group includes an alicyclic (meth)acrylate, the content of the alicyclic (meth)acrylate may be 40 to 90 mass%, 50 to 85 mass%, or 60 to 80 mass%, based on the mass of the monomer having a polymerizable unsaturated group. When the content of the alicyclic (meth)acrylate is 40 mass% or more, the elastic modulus of the cured product can be increased, and the strength of the cured product tends to be ensured. When the content of the alicyclic (meth)acrylate is 80 mass% or less, the elastic modulus of the cured product tends to be prevented from becoming too high.

[0051] [Phosphate compounds] The resin composition may further contain a phosphoric acid compound. The phosphoric acid compound is a compound having at least one selected from a phosphoric acid group and a phosphoric acid ester group, and at least one polymerizable unsaturated group. Examples of the polymerizable unsaturated group contained in the phosphoric acid compound include groups having a carbon-carbon double bond, such as a vinyl group (ethenyl group), an ethynyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamino group. The phosphoric acid compound preferably has a (meth)acryloyloxy group.

[0052] The phosphoric acid compound is preferably ethylene oxide-modified di(meth)acrylate phosphoric acid and / or propylene oxide-modified di(meth)acrylate phosphoric acid, and more preferably ethylene oxide-modified di(meth)acrylate phosphoric acid.

[0053] Examples of the phosphoric acid compound include compounds represented by the following formula (1), such as acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, acid phosphooxybutyl (meth)acrylate, acid phosphooxypentyl (meth)acrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, and acid phosphooxypolyoxypropylene glycol monomethacrylate.

[0054] [ka]

[0055] In the formula, R 1 represents hydrogen or a methyl group, R 2 represents a linear, branched, or cyclic alkyl group, n represents a number of 1 or more, and m represents a number of 1 to 3. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9, and even more preferably 1 to 6. n is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. m is preferably 1 or 2, and more preferably 1.

[0056] Examples of the phosphoric acid compound include 3-chloro-2-acid phosphooxypropyl (meth)acrylate, phenyl(2-(meth)acryloyloxyethyl)phosphate, diphenyl(2-(meth)acryloyloxyethyl)phosphate, (meth)acryloyloxy-2-hydroxypropyl acid phosphate, (meth)acryloyloxy-3-hydroxypropyl acid phosphate, (meth)acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, allyl alcohol acid phosphate, etc. The (C) phosphoric acid compound may be a salt thereof, such as a monomethanolamine salt or a monoethanolamine salt.

[0057] When the resin composition contains a phosphoric acid compound, the content of the phosphoric acid compound is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, based on the total mass of the resin and the monomer having a polymerizable unsaturated group, from the viewpoint of obtaining good adhesion to the substrate. The content of the phosphoric acid compound is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the total mass of the resin and the monomer having a polymerizable unsaturated group, from the viewpoint of maintaining the stability of the resin composition.

[0058] [Photopolymerization initiator] The resin composition may be a photocurable resin composition. The photocurable resin composition may contain a photopolymerization initiator. Photopolymerization initiators also include those called sensitizers. Specific examples of photopolymerization initiators include acridine; acridine-based compounds having at least one acridinyl group in the molecule; benzophenone; N,N-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone); aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanone-1, and (1-hydroxycyclohexyl)phenylmethanone; quinones such as alkylanthraquinone; benzoin ether compounds such as benzoyl alkyl ether; benzoyl alkyl ethers; Examples of suitable photopolymerization initiators include benzoin, benzoin compounds such as alkylbenzoin, benzil derivatives such as benzil dimethyl ketal, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, as well as 2,4,5-triarylimidazole dimers such as N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, and onium salts. Aromatic ketones are preferred for achieving a good balance between the deep curability and surface curability of the resin composition. Photopolymerization initiators can be used singly or in combination.

[0059] The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on the mass of the resin, from the viewpoint of sufficiently curing the surface of the photocurable resin composition and suppressing tackiness of the cured product. The content of the photopolymerization initiator is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the mass of the resin, from the viewpoint of obtaining sufficient curability and adhesion to deep portions.

[0060] [Additives] The resin composition may contain various additives as needed. Examples of additives include colorants, polymerization inhibitors, light stabilizers, antifoaming agents, fillers, antioxidants, chain transfer agents, thixotropy-imparting agents, plasticizers, flame retardants, mold release agents, surfactants, lubricants, and antistatic agents. Known additives can be used as these additives. The additives can be used alone or in combination of two or more.

[0061] [Manufacturing method] The resin composition can be produced by mixing the resin, the silane coupling agent (a), the compound (b), and, if necessary, a monomer having a polymerizable unsaturated group, a phosphoric acid compound, a photopolymerization initiator, and / or additives by stirring. Stirring can be performed by a known method using a stirrer, a stirring blade, etc. The temperature during stirring can be, for example, 60 to 90°C.

[0062] <Paint> The resin composition can be used, for example, as a coating material. The coating material contains at least a resin, a silane coupling agent (a), and a compound (b), and may also contain a monomer having a polymerizable unsaturated group, a phosphoric acid compound, a photopolymerization initiator, and / or an additive, as necessary.

[0063] <Cured product> According to an embodiment of the present invention, a cured product can be obtained using the above-described resin composition. The cured product may be in the form of a film. A cured product in the form of a film can be used as a protective film. For example, the cured product can be obtained by a manufacturing method including applying a resin composition and curing the applied resin composition by light irradiation. Examples of application methods include potting, dipping, spraying, roll coating, dispensing, and printing. Examples of curing methods include irradiation with ultraviolet light using a light source such as an LED lamp, a mercury lamp (low pressure, high pressure, ultra-high pressure, etc.), a metal halide lamp, an excimer lamp, or a xenon lamp.

[0064] <Electronic components> According to an embodiment of the present invention, electronic components having the above-described cured product can be obtained. Examples of electronic components include microcomputers, transistors, capacitors, resistors, relays, transformers, etc., mounted circuit boards on which these components are mounted, and lead wires, harnesses, film substrates, etc. that are joined to these electronic components. [Example]

[0065] The embodiments of the present invention will be described in more detail with reference to examples, but the embodiments of the present invention are not limited to the following examples.

[0066] <Preparation of Resin Composition> [Example 1] A resin composition was obtained by stirring 45 parts by mass of the following resin; 40 parts by mass of isobornyl acrylate, 10 parts by mass of dodecyl acrylate (lauryl acrylate), and 5 parts by mass of 1,10-decanediol diacrylate as monomers having a polymerizable unsaturated group; 1.5 parts by mass of the following polymerization initiator; 3 parts by mass of 3-acryloxypropyltrimethoxysilane as silane coupling agent (a); and 7 parts by mass of 3-isocyanatepropyltriethoxysilane as compound (b) while heating at 60°C.

[0067] resin [ka]

[0068] polymerization initiator [ka]

[0069] The ΔG of the methoxysilyl group in 3-acryloxypropyltrimethoxysilane (alkoxysilyl group (A) in the silane coupling agent (a)) and the ethoxysilyl group and isocyanate group in 3-isocyanatepropyltriethoxysilane (hydrolyzable group (B) in the compound (b)) are −3 kJ / mol, −18 kJ / mol, and −94 kJ / mol, respectively.

[0070] [Comparative Example 1] A resin composition was obtained in the same manner as in Example 1, except that 3-isocyanatepropyltriethoxysilane was not used.

[0071] Comparative Example 2 A resin composition was obtained in the same manner as in Example 1, except that 3-acryloxypropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane were not used.

[0072] <Evaluation of storage stability of resin composition> [Resin composition after storage 29 Si NMR spectrum] To accelerate deterioration over time, 1.4 molar equivalents of water relative to compound (a) were added to the prepared resin compositions, and the resin compositions were stored at 60°C for 60 hours. 29 Si NMR spectrum measurement was carried out.

[0073] Figure 1 shows: 29 The Si NMR spectrum shows that, after storage, peaks (T1, T2, and T3 peaks) of the polymer of 3-acryloxypropyltrimethoxysilane (silane coupling agent (a)) were detected in the resin composition of Comparative Example 1, whereas in the resin composition of Example 1, no polymer peaks were detected, and peaks of 3-acryloxypropyltrimethoxysilane (silane coupling agent (a)) and 3-isocyanatepropyltriethoxysilane (compound (b)) were detected. From the above results, it is clear that the inclusion of compound (b) suppresses the hydrolysis of silane coupling agent (a).

[0074] [Adhesion of the cured product] Cured products were prepared by the following method using the resin compositions of Comparative Examples 1 and 2 after preparation and the resin compositions of Example 1 and Comparative Example 1 after storage, and their adhesiveness was evaluated. (Preparation of cured product) The resin composition was applied onto a glass substrate using a jet dispenser E4 manufactured by Nordson EFD, and then irradiated with ultraviolet light (integrated light amount: 300 mJ / cm 2 ), and a cured product with a film thickness of 0.18 mm and a width of 1.0 to 1.4 mm was prepared. (Peel strength measurement) Adhesion was evaluated by a 90-degree peel test. Peel strength was measured using an Autograph EZ-S manufactured by Shimadzu Corporation at a test speed of 50 mm / min and a data processing range of 20 to 40 mm.

[0075] (Evaluation results) The peel strength of the cured product prepared using the prepared resin composition was 225 N / m in Comparative Example 1 and 67 N / m in Comparative Example 2. The resin composition containing the silane coupling agent (a) had a peel strength that was approximately 3.4 times higher than that of the resin composition not containing the silane coupling agent (a). The peel strength of the cured product prepared using the resin composition after storage was 135 N / m in Example 1 and 39 N / m in Comparative Example 1. The resin composition containing the silane coupling agent (a) and the compound (b) had a peel strength that was approximately 3.5 times higher than that of the resin composition containing the silane coupling agent (a) but not the compound (b). It is clear that the resin composition containing the silane coupling agent (a) but not the compound (b) has improved adhesive strength immediately after preparation, but the adhesive strength decreases over time, and the storage stability is insufficient. In contrast, the resin composition containing the silane coupling agent (a) and the compound (b) maintains the effect of improving adhesive strength even after aging, and has excellent storage stability.

[0076] [Reliability of electronic components] Using the resin compositions of Comparative Examples 1 and 2 after production and the resin compositions of Example 1 and Comparative Example 1 after storage, protective films for protecting electrodes on wiring boards were formed by the following method, and the electrodes after accelerated aging were observed to evaluate the presence or absence of corrosion. (Protective Film Formation) An ITO comb-shaped electrode substrate (L / S=35 μm / 15 μm, 15 mm × 130 mm × 0.7 mm, Corning E-XG 0.7t manufactured by Corning Incorporated) was prepared. Figure 2 shows a schematic diagram of the ITO comb-shaped electrode substrate. The resin composition was applied to the ITO comb-shaped electrode substrate, and ultraviolet light (light source: LED 365 nm, cumulative light intensity: 300 mJ / cm ) was applied using a Panasonic UD40 Curing System. 2 ) to cure the resin composition, forming a protective film with a thickness of 50 μm. (Observation of electrodes after current application) A test specimen was created in which the cleaning agent was immersed inside the protective film by adhesively attaching a chip filled with cleaning agent to a protective film formed on an ITO comb-shaped electrode substrate. Figure 3 shows a schematic external view, a schematic overhead view, and a schematic cross-sectional view of the test specimen. Using an Espec SH-661, a DC 10V current was applied to the test specimen at room temperature for 168 hours. The electrodes were visually inspected after the current was applied.

[0077] (Evaluation results) In the electrode provided with the protective film prepared using the prepared resin composition, corrosion was suppressed after energization in Comparative Example 1, but the electrode was entirely corroded after energization in Comparative Example 2. By using a resin composition containing a silane coupling agent (a), the reliability of the substrate could be improved. In the electrode provided with a protective film prepared using the resin composition after storage, corrosion was suppressed after application of current in Example 1, but the electrode was entirely corroded after application of current in Comparative Example 1. By using a resin composition containing the silane coupling agent (a) and the compound (b), it was possible to improve the reliability of the substrate even after storage of the resin composition. It is clear that a resin composition containing a silane coupling agent (a) but not a compound (b) can improve the reliability of electronic components immediately after production, but the effect of improving reliability is lost over time, and the storage stability is insufficient.In contrast, a resin composition containing a silane coupling agent (a) and a compound (b) can improve the reliability of electronic components even after aging, and has excellent storage stability.

Claims

1. The composition contains a resin, a silane coupling agent having an alkoxysilyl group (A), and a compound having a hydrolyzable group (B), a Gibbs free energy change ΔGa when the alkoxysilyl group (A) reacts with water and a Gibbs free energy change ΔGb when the hydrolyzable group (B) reacts with water satisfy the relationship ΔGa−ΔGb>0 kJ / mol, the resin includes a resin having a polymerizable unsaturated group, the silane coupling agent further has a (meth)acryloyl group, the alkoxysilyl group (A) contains a trimethoxysilyl group, the hydrolyzable group (B) contains an isocyanate group and an alkoxysilyl group, Further containing a monomer having a polymerizable unsaturated group, Resin composition.

2. The resin composition according to claim 1 , wherein the polymerizable unsaturated group of the monomer includes a (meth)acryloyl group.

3. The resin composition according to claim 1 or 2, which is a photocurable resin composition.

4. The resin composition according to any one of claims 1 to 3, which is a paint.

5. A cured product obtained using the resin composition according to any one of claims 1 to 4.

6. An electronic component comprising the cured product according to claim 5 .

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