Novel (METH)acrylamide, composition containing same, curable composition, adhesive agent, sealing material, cured article, semiconductor device, and electronic component

Abstract

The present invention addresses the problem of providing: a novel substance which is capable of solving the problems of conventional bismaleimides each having a dimer acid skeleton; a high-concentration composition of the substance; a curable composition which contains the composition; an adhesive agent or a sealing material; a cured article obtained by curing the composition or the like; and a semiconductor device or an electronic component which includes the cured article.　Provided are: a dimer acid-modified N-substituted (meth)acrylamide; a high-concentration composition of the dimer acid-modified N-substituted (meth)acrylamide; a curable composition which contains the composition; an adhesive agent or a sealing material; a cured article obtained by curing the composition or the like; and a semiconductor device or an electronic component which includes the cured article.

Description

Novel (meth)acrylamide, composition containing the same, curable composition, adhesive, sealant, cured product, semiconductor device, and electronic component

[0001] The present invention relates to a novel (meth)acrylamide, a composition containing the same, a curable composition, an adhesive or a sealant containing the same, a cured product thereof, and a semiconductor device or an electronic component containing the cured product.

[0002] Currently, for the assembly and mounting of electronic components used in semiconductor devices, such as semiconductor chips, adhesives, sealants, etc. containing curable resin compositions are often used for the purpose of maintaining reliability.

[0003] As a resin composition used for such adhesives and sealants for electronic components, for example, a resin composition containing polymaleimide is known. Polymaleimide having two or more maleimide groups can be photocured and thermally cured by radical polymerization, ionic polymerization, etc. of the double bond contained in the maleimide group, addition reaction with hydrogen of aromatic amine, copolymerization with allylphenol, etc., gives a cured product with excellent heat resistance, and is known to obtain good adhesive strength due to its high polarity. On the other hand, polymaleimide has a high crystallinity and has a problem that it is difficult to perform melting or dissolution in order to ensure moldability when used as a curable composition because of its high melting point and low solubility in organic solvents. In addition, there is a concern that many commercially available cured products of polymaleimide have a high water absorption rate and are inferior in moisture resistance reliability.

[0004] Patent Document 1 discloses an adhesive containing a bismaleimide compound into which a dimer acid skeleton, etc. is introduced. Substances mainly containing such a bismaleimide having a dimer acid skeleton are commercially available, and examples include BMI-689, BMI-1500, BMI-1700, etc. manufactured by Designer molecules.

[0005] U.S. Patent Application Publication No. 2010 / 0063184

[0006] Bismaleimides having a dimer acid skeleton exhibit reactivity derived from the maleimide group and can be polymerized by light irradiation in or out of the presence of a photoradical generator, or by heating in the presence of a thermal radical generator. Furthermore, due to the dimer acid skeleton, they offer the advantages of excellent moisture resistance and the ability to produce flexible (low-elasticity) cured products. However, it has been found that bismaleimides having a dimer acid skeleton still suffer from insufficient adhesive strength in both photocuring and thermal curing, as well as insufficient photocuring depth. The inventors have discovered a dimer acid-modified acrylamide that can overcome these problems with bismaleimides having a dimer acid skeleton, and have filed patent applications relating to this dimer acid-modified acrylamide, a curable composition containing it, an adhesive or encapsulant, cured products obtained by curing them, and semiconductor devices or electronic components containing the cured products (Japanese Patent Application No. 2023-060069, PCT / JP2024 / 013411, and Taiwan Patent Application No. 113112395). Dimer acid-modified acrylamide is a substance in which an acrylamide group is bonded to a hydrocarbon group derived from dimer acid, and is, for example, a mixture containing several diacrylamide compounds (but not limited to these) in any proportion. Compared to curable compositions containing bismaleimide having a dimer acid skeleton, curable compositions can provide cured products with higher adhesive strength after curing and / or thermal curing, a greater photocuring depth, and superior reliability.

[0007] On the other hand, the dimer acid-modified acrylamide has a viscosity tens of times higher than bismaleimide, which has a dimer acid skeleton, making it difficult to handle. Furthermore, it was found that the medium could not be completely removed during purification after production, resulting in residual medium. In addition, because the dimer acid-modified acrylamide is amphiphilic, the two phases are difficult to separate and tend to mix when attempting to remove water-soluble impurities by liquid-liquid extraction, resulting in poor purification efficiency.

[0008] The present invention aims to provide a novel substance, a high-concentration composition thereof, a curable composition containing the same, an adhesive or encapsulant, a cured product obtained by curing them, and a semiconductor device or electronic component containing the cured product, which can solve the problems of bismaleimide having the above-mentioned dimer acid skeleton.

[0009] The specific means for solving the above-mentioned problems are as follows. The embodiments of the present invention include the following novel (meth)acrylamides, compositions containing the (meth)acrylamide, curable compositions, adhesives or sealants, cured products, and semiconductor devices or electronic components. [1] The following formula (I): -NR １ C(O)CR ２ =CH ２ ...(I) (wherein, R １ R is an organic group with a formula weight of 110 or less. ２ (where is hydrogen or methyl.) Dimer acid-modified N-substituted (meth)acrylamide having an N-substituted (meth)acrylamide group represented by [2]R １The dimer acid-modified N-substituted (meth)acrylamide according to [1], wherein the organic group is selected from the group consisting of optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, optionally substituted acyl groups, optionally substituted cycloalkyl groups, optionally substituted cycloalkenyl groups, optionally substituted aliphatic heterocyclic groups, optionally substituted aryl groups, and optionally substituted heteroaryl groups, and has a formula weight of 110 or less. [3] A composition comprising the dimer acid-modified N-substituted (meth)acrylamide according to [1] or [2] and a polymerization inhibitor, wherein the content of the dimer acid-modified N-substituted (meth)acrylamide in the composition is 99% by weight or more. [4] A curable composition comprising the dimer acid-modified N-substituted (meth)acrylamide according to [1] or [2] and a radical polymerization initiator. [5] The curable composition according to [4], wherein the radical polymerization initiator is a photoradical polymerization initiator. [6] The curable composition according to [4], wherein the radical polymerization initiator is a thermal radical polymerization initiator. [7] The curable composition according to any one of [4] to [6], further comprising a curable component other than the dimer acid-modified N-substituted (meth)acrylamide. [8] The curable composition according to any one of [4] to [7], wherein the dimer acid-modified N-substituted (meth)acrylamide and the radical polymerization initiator are contained in a single container. [9] The curable composition according to any one of [4] to [7], wherein the dimer acid-modified N-substituted (meth)acrylamide and the radical polymerization initiator are contained in two or more containers.

[10] An adhesive or sealant comprising the curable composition according to any one of [4] to [9].

[11] A cured product obtained by curing the curable composition according to any one of [4] to [9], or the adhesive or sealant according to

[10] .

[12] A semiconductor device or electronic component comprising the cured product according to

[11] .

[0010] According to an aspect of the present invention, there are provided a dimer acid-modified N-substituted (meth)acrylamide capable of solving the problems of bismaleimide having a dimer acid skeleton, a high-concentration composition thereof, a curable composition, an adhesive or a sealant containing the same, a cured product thereof, and a semiconductor device or an electronic component including the cured product. The curable composition containing the dimer acid-modified N-substituted (meth)acrylamide has a higher adhesive strength and a higher photo-curing depth after photo-curing and / or heat-curing as compared with a curable composition containing bismaleimide having a dimer acid skeleton, and thus can provide a cured product excellent in reliability.

[0011] It is an example of the mass spectrum of the dimer acid-modified N-methylacrylamide composition (A-1) of Production Example 1.

[0012] [Novel (meth)acrylamide and composition containing the same] One aspect of the present invention is represented by the following formula (I): -NR １ C(O)CR ２ =CH ２ ... (I) (In the formula, R １ is an organic group having a formula weight of 110 or less, and R ２ is hydrogen or methyl.) It is a dimer acid-modified N-substituted (meth)acrylamide having an N-substituted (meth)acrylamide group. Another aspect of the present invention is a composition containing the dimer acid-modified N-substituted (meth)acrylamide of the above aspect and a polymerization inhibitor, and in the composition, the content of the dimer acid-modified N-substituted (meth)acrylamide is 99% by weight or more. According to these aspects, a novel dimer acid-modified N-substituted (meth)acrylamide and a high-concentration composition of the dimer acid-modified N-substituted (meth)acrylamide are provided. By using this dimer acid-modified N-substituted (meth)acrylamide or the dimer acid-modified N-substituted (meth)acrylamide composition, it becomes possible to prepare a curable composition containing the dimer acid-modified N-substituted (meth)acrylamide. In the present specification, "(meth)acrylamide" refers to both acrylamide and methacrylamide.

[0013] Dimer acid is a liquid fatty acid that primarily contains a dibasic acid of C36 dicarboxylic acid produced by the dimerization of C18 unsaturated fatty acids derived from plant-based oils and fats, and may contain arbitrary amounts of C18 unsaturated fatty acids (sometimes called C18 monomeric acids), C54 trimer acid, and other polymerized fatty acids. Examples of C18 unsaturated fatty acids include oleic acid, linoleic acid, and linolenic acid. C36 dicarboxylic acids mainly include acyclic, monocyclic, polycyclic, and aromatic ring compounds represented by the structural formulas shown below. The C36 dicarboxylic acid in dimer acid may be a mixture containing multiple C36 dicarboxylic acid compounds in arbitrary proportions, depending on the plant raw materials and manufacturing method. Furthermore, while dimer acids retain double bonds (C=C) after the polymerization reaction of unsaturated fatty acids, in this specification, hydrogenated products obtained by further hydrogenation to reduce the degree of unsaturation are also included in the definition of dimer acid. In addition, dimer acid may contain arbitrary amounts of C18 monomeric acid, C54 trimer acid, other polymerized fatty acids, etc., depending on the manufacturing method, degree of purification, etc. In this specification, dimer acid may contain these monomeric acid, trimer acid, other polymerized fatty acids, etc.

[0014] In this specification, the following formula (I): -NR １ C(O)CR ２ =CH ２ ...(I) (wherein, R １ R is an organic group with a formula weight of 110 or less. ２ Dimer acid-modified N-substituted (meth)acrylamide having an N-substituted (meth)acrylamide group represented by (where is hydrogen or methyl) (hereinafter also referred to as "dimer acid-modified N-substituted (meth)acrylamide") is defined as a dimer acid-modified N-substituted (meth)acrylamide group having a terminal carboxyl group (-COOH) of the dimer acid (-CH ２ -NR １ C(O)CR ２ =CH ２ This refers to a substance in which a hydrocarbon group derived from dimer acid has been replaced by an N-substituted (meth)acrylamide group (-NR １ C(O)CR ２ =CH２ It can also be said that it is a substance to which a ) is bonded. In other words, in this specification, "dimer acid modified N-substituted (meth)acrylamide" always contains di-N-substituted (meth)acrylamide derived from C36 dicarboxylic acid as the main component, and may contain (i.e., may or may not contain) arbitrary amounts of mono-N-substituted (meth)acrylamide derived from C18 monomeric acid, tri-N-substituted (meth)acrylamide derived from C54 trimer acid, and N-substituted (meth)acrylamide derived from other polymerizable fatty acids. In this specification, "hydrocarbon group derived from dimer acid" means that the terminal carboxyl group (-COOH) of the dimer acid is a methylene group (-CH ２ This refers to a hydrocarbon group that has been substituted with a -, and is also called a "dimer acid skeleton".

[0015] Examples of di-N-substituted (meth)acrylamides in dimer acid-modified N-substituted (meth)acrylamides include, but are not limited to, the following: The formula is as follows: An acyclic form represented by the following equation: A monocyclic form represented by the following formula: A polycyclic form represented by the following formula: Aromatic ring type represented by [this symbol].

[0016] In equation (I), R １ This refers to organic groups with a formula weight of 110 or less. Specifically, R １ This is an organic group with a formula weight of 110 or less, selected from the group consisting of optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, optionally substituted acyl groups, optionally substituted cycloalkyl groups, optionally substituted cycloalkenyl groups, optionally substituted aliphatic heterocyclic groups, optionally substituted aryl groups, and optionally substituted heteroaryl groups.

[0017] Examples of alkyl groups include linear or branched alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, and octyl. Examples of alkenyl groups include linear or branched alkenyl groups having 2 to 8 carbon atoms, such as ethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, and 5-hexenyl. Examples of alkynyl groups include linear or branched alkynyl groups having 2 to 8 carbon atoms, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, and 4-methyl-2-pentynyl. Examples of acyl groups include alkyl-CO- groups in which the alkyl group is bonded to a carbonyl group, such as acetyl, propionyl, pivaloyl, butanoyl, pentanoyl, hexanoyl, and heptanoyl. Examples of cycloalkyl groups include saturated monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. A cycloalkyl group can have one bond to an amide nitrogen at any substituted position. Examples of cycloalkenyl groups include cyclic groups that contain one or more double bonds in part of the ring of the saturated cycloalkyl group. Examples include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl, where one of the carbon bonds constituting the ring is a double bond. A cycloalkenyl group can have one bond to an amide nitrogen at any substituted position.An aliphatic heterocyclic group is a saturated or partially unsaturated, 3-8 membered monocyclic aliphatic heterocyclic group containing 1 to 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen, and sulfur in addition to carbon atoms as ring constituent atoms. Specifically, examples include azilidinyl, oxyranyl, thyranyl, azetidinyl, oxetanyl, thietanyl, tetrahydrothienyl, tetrahydrofuranyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, oxazolinyl, oxazolidinyl, pyrazolinyl, pyrazolidinyl, thiazolinyl, and thiazolidinyl. An aliphatic heterocyclic group can have one bond with an amide nitrogen at any substituted position, and the bond may be on either a carbon atom or a nitrogen atom. Examples of aryl groups include aryl groups with 6 or fewer carbon atoms, such as the phenyl group. Examples of heteroaryl groups include monocyclic heteroaryl groups that contain 1 to 4 identical or different heteroatoms selected from nitrogen, oxygen, and sulfur atoms in addition to carbon atoms as ring constituent atoms, and have 5 to 7 constituent atoms in the ring. Specifically, examples include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridadinyl. Heteroaryl groups can have one bond at any substituted position, and the bond may be on either a carbon atom or a nitrogen atom. Examples of substituents on alkyl groups, alkenyl groups, alkynyl groups, and acyl groups include optionally substituted cycloalkyl groups, optionally substituted cycloalkenyl groups, optionally substituted aliphatic heterocyclic groups, optionally substituted aryl groups, and optionally substituted heteroaryl groups. For example, benzyl is an example of a substituted alkyl group. Substituents for cycloalkyl groups, cycloalkenyl groups, and aliphatic heterocyclic groups include optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, and oxo groups.Substituents for the optionally substituted aryl group and optionally substituted heteroaryl group include optionally substituted alkyl groups, optionally substituted alkenyl groups, and optionally substituted alkynyl groups.

[0018] In one embodiment, R １ This is an organic group with a formula weight of 110 or less, selected from the group consisting of optionally substituted alkyl groups, optionally substituted alkenyl groups, and optionally substituted aryl groups. In one embodiment, R １ is methyl, ethyl, propyl, isopropyl, 2-propenyl, benzyl, or phenyl. In one embodiment, R １ is methyl, ethyl, 2-propenyl, or benzyl. In one embodiment, R １ It is methyl.

[0019] In one embodiment, R ２ is hydrogen. In one embodiment, R ２ It is methyl.

[0020] In one embodiment, R １ R is an organic group with a formula weight of 110 or less, selected from the group consisting of optionally substituted alkyl groups, optionally substituted alkenyl groups, and optionally substituted aryl groups. ２ is hydrogen. In one embodiment, R １ is methyl, ethyl, propyl, isopropyl, 2-propenyl, benzyl, or phenyl, and R ２ is hydrogen. In one embodiment, R １ is methyl, ethyl, 2-propenyl, or benzyl, R ２ is hydrogen. In one embodiment, R １ is methyl, and R ２ is hydrogen. In one embodiment, R １ R is an organic group with a formula weight of 110 or less, selected from the group consisting of optionally substituted alkyl groups, optionally substituted alkenyl groups, and optionally substituted aryl groups. ２is methyl. In one embodiment, R １ is methyl, ethyl, propyl, isopropyl, 2-propenyl, benzyl, or phenyl, and R ２ is methyl. In one embodiment, R １ is methyl, ethyl, 2-propenyl, or benzyl, R ２ is methyl. In one embodiment, R １ is methyl, and R ２ It is methyl.

[0021] Dimer acid-modified acrylamide, in which an acrylamide group is bonded to a hydrocarbon group derived from dimer acid, exhibits high viscosity. This is presumed to be due to intramolecular and intermolecular hydrogen bonding between the amide proton and carbonyl oxygen of acrylamide, as shown below. Therefore, when the amide proton of dimer acid-modified acrylamide was substituted with an organic group, the resulting dimer acid-modified N-substituted (meth)acrylamide exhibited lower viscosity compared to dimer acid-modified acrylamide. In one embodiment, the viscosity of dimer acid-modified N-substituted (meth)acrylamide is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, even more preferably 20 Pa·s or less, particularly preferably 10 Pa·s or less, and most preferably 5 Pa·s or less at 25°C and a rotation speed of 5 rpm. In this specification, viscosity refers to the value measured at a measurement temperature of 25°C using an appropriate viscometer (e.g., an E-type viscometer) depending on the viscosity range. Furthermore, compared to dimer acid-modified acrylamide, the residual solvent of dimer acid-modified N-substituted (meth)acrylamide could be removed in fewer steps after production, and a high concentration could be obtained. This is thought to be because, unlike dimer acid-modified acrylamide, dimer acid-modified N-substituted (meth)acrylamide does not have hydrogen bond donors, and therefore has little to no interaction with the solvent in terms of hydrogen bonding. The resulting high-concentration composition of dimer acid-modified N-substituted (meth)acrylamide has the advantage of meeting the demand for low VOC (volatile organic compound) content in the manufacturing industry. Furthermore, because the polarity of the amide group is shielded by the N-substituent, lipophilicity is increased, improving extraction efficiency after manufacturing and making it possible to easily wash away salts and water-soluble impurities. In addition, it was confirmed that the curable composition containing the obtained dimer acid-modified N-substituted (meth)acrylamide has higher adhesive strength after photocuring and / or thermal curing, and a higher photocuring depth, compared to a curable composition containing bismaleimide with a dimer acid skeleton. From the viewpoint of avoiding the decrease in reactivity of the (meth)acrylamide group due to steric hindrance, the organic group R １ The formula weight is 110 or less, preferably 100 or less, and more preferably 60 or less.

[0022] The content of di-N-substituted (meth)acrylamide, mono-N-substituted (meth)acrylamide, and tri-N-substituted (meth)acrylamide contained in dimer acid-modified N-substituted (meth)acrylamide depends on the raw materials and manufacturing / purification methods, and in one embodiment it may be 75-100% by weight, 0-5% by weight, and 0-25% by weight, respectively; in another embodiment it may be 90-100% by weight, 0-5% by weight, and 0-10% by weight, respectively; in yet another embodiment it may be 95-100% by weight, 0-5% by weight, and 0-5% by weight, respectively; and in yet another embodiment it may be 99-100% by weight, 0-1% by weight, and 0-1% by weight, respectively.

[0023] The method for producing dimer acid-modified N-substituted (meth)acrylamide is not particularly limited, but for example, Method A: (a1) A step of reacting a dimer amine and a (meth)acrylic acid halide in the presence or absence of a solvent, in the presence or absence of a base to obtain dimer acid-modified (meth)acrylamide, and (a2) the obtained dimer acid-modified (meth)acrylamide and R １ X (where R １ A method comprising the step of reacting (wherein the presence or absence of a solvent, or the presence or absence of a base) with (b1) a dimer acid modified bis-N-monosubstituted amine (wherein the presence or absence of an N-substituted atom is R) with a dimer acid modified bis-N-monosubstituted amine (wherein the presence or absence of an N-substituted atom is R) by reductive amination using various aldehydes and dimer amines, and a manufacturing method B: (b1) Dimer acid modified bis-N-monosubstituted amine (wherein the presence or absence of an N-substituted atom is R) １ And R １ A method is provided that includes the steps of (b) obtaining (the same as above), and (b) reacting the obtained dimer acid-modified bis-N-monosubstituted amine with a (meth)acrylic acid halide in the presence or absence of a solvent, in the presence or absence of a base, to obtain a dimer acid-modified N-substituted (meth)acrylamide.

[0024] In step (a1) of manufacturing method A, a dimer amine and a (meth)acrylic acid halide are reacted in the presence or absence of a solvent and in the presence or absence of a base to obtain dimer acid-modified (meth)acrylamide. The dimer amine used in step (a1) is a dimer acid in which the terminal carboxyl group (-COOH) is an aminomethyl group (-CH₂). ２ -NH ２Dimer amine is a substance substituted with a diamine, and may contain arbitrary amounts of monoamines, triamines, etc., in addition to the main component diamine. The content of monoamines and triamines in dimer amine depends on the raw materials and the manufacturing and purification methods. Commercial dimer amines include, but are not limited to, the trade names "PRIAMINE 1071," "PRIAMINE 1073," "PRIAMINE 1074," and "PRIAMINE 1075" (all manufactured by Cargill Japan LLC). For example, "PRIAMINE 1071" has a diamine content of approximately 75% by weight and a triamine content of approximately 25% by weight. For example, "PRIAMINE 1075" has a diamine content exceeding 99% by weight and a triamine content of less than 1% by weight. See Polymer, Vol. 205 (2020), 122768. Examples of (meth)acrylic acid halides used in step (a1) include (meth)acrylic acid chloride and (meth)acrylic acid bromide. The solvent used in step (a1) can be any solvent that does not affect this reaction, and examples include hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), halogenated solvents (dichloromethane, chloroform, etc.), etc., and these can also be used in appropriate combinations. Examples of bases used in step (a1) include, but are not limited to, triethylamine, pyridine, diisopropylethylamine, 2,6-lutidine, and 4-dimethylaminopyridine. This reaction can be carried out at 0°C to 50°C, preferably 10°C to 30°C.

[0025] In step (a2), the dimer acid-modified (meth)acrylamide obtained in step (a1) and R １ X (where R１ (This is the same as above, and X is a halogen atom.) is reacted with a base in the presence or absence of a solvent, in the presence or absence of a base, to obtain a dimer acid-modified N-substituted (meth)acrylamide. １ The halogen atom of X may be fluorine, chlorine, bromine, or iodine, with chlorine, bromine, or iodine being preferred. The solvent used in step (a2) may be any solvent that does not affect this reaction, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), halogenated solvents (dichloromethane, chloroform, etc.), etc., and these may be used in appropriate combinations. The base used in step (a2) may be an alkali metal or alkaline earth metal hydride (NaH, KH, CaH ２ (etc.), hydroxides of alkali metals or alkaline earth metals (CsOH, RbOH, LiOH, NaOH, KOH, Ca(OH)) ２ (e.g.), alkali metal or alkaline earth metal carbonates (Li ２ CO ３ Na ２ CO ３ _K ２ CO ３ , Cs ２ CO ３ CaCO ３ Examples include, but are not limited to, those listed above. This reaction can be carried out at 0°C to 50°C, preferably 10°C to 30°C.

[0026] In manufacturing method B, step (b1), dimer acid-modified bis-N-monosubstituted amines are produced by reductive amination using various aldehydes and dimer amines (where the N-substituent is R １ And R １(This is the same as above) is obtained. The dimer amine used in step (b1) is the same as the one used in step (a1). The aldehyde used in step (b1) includes not only aldehydes such as benzaldehyde, but also formic acid derivatives such as formic acid esters. Sodium borohydride is preferably used as the reducing agent in step (b1), but is not limited to this. For example, when formic acid ester is used as the aldehyde, lithium aluminum hydride (LiAlH) is used as the reducing agent. ４ It can be reduced to an amine by using )

[0027] In step (b2), the dimer acid-modified bis-N-monosubstituted amine obtained in step (b1) is reacted with a (meth)acrylic acid halide in the presence or absence of a solvent, and in the presence or absence of a base, to obtain a dimer acid-modified N-substituted (meth)acrylamide. Examples of (meth)acrylic acid halides used in step (b2) include (meth)acrylic acid chloride and (meth)acrylic acid bromide. The solvent used in step (b2) can be any solvent that does not affect the reaction, and examples include hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), halogenated solvents (dichloromethane, chloroform, etc.), etc., and these can also be used in appropriate combinations. Examples of bases used in step (b2) include, but are not limited to, triethylamine, pyridine, diisopropylethylamine, 2,6-lutidine, 4-dimethylaminopyridine, etc. This reaction can be carried out at 0°C to 50°C, preferably 10°C to 30°C.

[0028] Dimer acid-modified N-substituted (meth)acrylamide produced by manufacturing methods A and B can be separated and purified from the reaction mixture by conventional liquid-liquid extraction, removing salts and water-soluble impurities. After separation and purification, the organic layer containing the dimer acid-modified N-substituted (meth)acrylamide is subjected to vacuum distillation to remove the solvent. By appropriately adding a polymerization inhibitor at this time, the solvent can be easily removed while suppressing the occurrence of unintended radical reactions. As a result, the resulting dimer acid-modified N-substituted (meth)acrylamide composition has a content of 99% by weight or more of the dimer acid-modified N-substituted (meth)acrylamide in the composition. That is, another aspect of the present invention is a composition comprising the dimer acid-modified N-substituted (meth)acrylamide of the above aspect and a polymerization inhibitor, wherein the content of the dimer acid-modified acrylamide in the composition is 99% by weight or more. In one embodiment, the dimer acid-modified N-substituted (meth)acrylamide composition does not contain a solvent. In one embodiment, the composition comprises a dimer acid-modified N-substituted (meth)acrylamide as described above and a polymerization inhibitor.

[0029] The polymerization inhibitor can be any known polymerization inhibitor, such as amine-based radical polymerization inhibitors like N-nitroso-N-phenylhydroxylamine aluminum (NNAS) and phenothiazine; triphenylphosphine; phenol-based polymerization inhibitors like p-methoxyphenol and 2,6-di-t-butyl-4-methylphenol; and hydroquinone-based polymerization inhibitors like hydroquinone, methoxyhydroquinone, and di-t-butylhydroquinone, but is not limited to these. Furthermore, known radical polymerization inhibitors disclosed in Japanese Patent Publication No. 2010-117545 and Japanese Patent Publication No. 2008-184514 can also be used. Any one radical polymerization inhibitor may be used, or two or more may be used in combination. Among these, amine-based polymerization inhibitors such as N-nitroso-N-phenylhydroxylamine aluminum (NNAS) and phenothiazine are preferred. The content of the polymerization inhibitor in the composition may be, for example, 0.001 to 1% by weight.

[0030] [Curable Composition] A curable composition according to one aspect of the present invention comprises a dimer acid-modified N-substituted (meth)acrylamide and a radical polymerization initiator according to the above aspect. According to this aspect, a curable composition can be provided that exhibits excellent adhesive strength after photocuring and / or thermal curing, and has a good photocuring depth.

[0031] Since the dimer acid-modified N-substituted (meth)acrylamide contained in the curable composition is the same as the dimer acid-modified N-substituted (meth)acrylamide in the above embodiment, the description of dimer acid-modified N-substituted (meth)acrylamide in the above embodiment also applies to this embodiment. The content of dimer acid-modified N-substituted (meth)acrylamide in the curable composition is, for example, 1% by weight or more and less than 100% by weight, for example, 5 to 98% by weight.

[0032] Examples of radical polymerization initiators include photo-radical polymerization initiators and thermal radical polymerization initiators. In one embodiment, the radical polymerization initiator is a photo-radical polymerization initiator. In one embodiment, the radical polymerization initiator is a thermal radical polymerization initiator. In one embodiment, the radical polymerization initiator includes both a photo-radical polymerization initiator and a thermal radical polymerization initiator.

[0033] The inclusion of a photoradical polymerization initiator accelerates the photocuring of the curable composition. The type of photoradical polymerization initiator is not particularly limited, and known materials can be used. Examples of photoradical polymerization initiators include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive site and a peroxide structure. Maleimide compounds can also be used as photoradical polymerization initiators.

[0034] Examples of alkylphenone compounds include benzyldimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (commercially available as Omnirad from IGM Resins B.V.) Examples include, but are not limited to, 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone (commercially available as Omnirad 369 from IGM Resins B.V.).

[0035] Examples of acylphosphine oxide compounds include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (commercially available as Omnirad TPO H from IGM Resins B.V.) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 from IGM Resins B.V.).

[0036] Examples of oxime ester compounds include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane,4-(2-methoxyphenoxy)-9H-carbazole-3-yl]-,1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA). These may be used individually or in combination of two or more.

[0037] Examples of compounds having a photosensitive site and a peroxide structure, or commercially available products thereof, include, but are not limited to, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation).

[0038] Other examples of photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyldimethyl ketal, and benzo Examples include, but are not limited to, phenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, and camphorquinone.

[0039] Maleimide compounds are activated by light to generate radicals, which promote the polymerization of radically polymerizable compounds. In other words, maleimide compounds are polymerizable compounds and can also function as photoradical polymerization initiators. Examples of maleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimoidphenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimide hexane, and 1,2-bismaleimide ethane (N,N'-ethylenedimaleimide). Examples of bismaleimides having a dimer acid skeleton include, but are not limited to, N,N'-(1,2-phenylene)bismaleimide, N,N-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide, N,N'-[4,4'-(1,3-phenylenedioxy)diphenyl]bismaleimide, 4,4'-dimaleimide phenyl ether, and bismaleimides having a dimer acid skeleton. Examples of commercially available bismaleimides having a dimer acid skeleton include, but are not limited to, product names "BMI-689", "BMI-1500", "BMI-1700", or "BMI-3000" (all manufactured by Designer Molecules Inc.). These can be used individually, or two or more can be used in combination.

[0040] The photoradical polymerization initiator may be used individually or in combination of two or more types.

[0041] The content of the photoradical polymerization initiator is preferably 0.01 to 10% by weight, and more preferably 0.04 to 8% by weight, relative to the total weight of the curable composition, from the viewpoint of curing rate and pot life of the curable composition.

[0042] By incorporating a thermal radical polymerization initiator into the curable composition, it becomes possible to cure the composition with short heating time. The type of thermal radical polymerization initiator is not particularly limited, and known materials can be used. Specific examples of thermal radical polymerization initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, and 2,2-bis(t-butyl Examples of peroxyketals include peroxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, ethyl 3,3-(t-butylperoxy)butyrate, and alkylperoxyesters such as t-butylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, and t-butylperoxybenzoate, but are not limited to these. Various thermal radical polymerization initiators may be used individually or in combination of two or more.

[0043] If a thermal radical polymerization initiator is included, the content of the thermal radical polymerization initiator is preferably 0.01 to 10% by weight, more preferably 0.1 to 8% by weight, based on the total weight of the curable composition.

[0044] The curable composition of this embodiment may contain a reactive diluent, to the extent that it does not impair the effects of the present invention. The reactive diluent has a reactive group and reacts with the curable component during curing to be incorporated into the molecule, thereby minimizing the degradation of the performance of the curable composition. The reactive diluent is not particularly limited, and known materials can be used, but from the viewpoint of reactivity with the (meth)acryloyl group of dimer acid-modified N-substituted (meth)acrylamide, a (meth)acrylate compound or maleimide compound having a viscosity of 1 Pa·s or less at 25°C can be preferably used.

[0045] Examples of (meth)acrylate compounds as reactive diluents include ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, and Phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, 3,3,5-Trimethylcyclohexyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 1-naphthalene methyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate Nonylphenoxypolyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate 2-ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropane-2 -yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2-furanyl (meth)acrylate, 2-oxotetrahydrofuran-3-yl (meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl (meth)acrylate, (2-oxo-1,Examples of such acrylates include, but are not limited to, 3-dioxolan-4-yl)methyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, tricyclodecane dimethanol (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, PEG-modified di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, glycerin propoxytri(meth)acrylate, pentaerythritol alkoxytetra(meth)acrylate, and pentaerythritol (tri / tetra)(meth)acrylate. These may be used individually or in combination of two or more. In this specification, "(meth)acrylate compound" refers to both acrylate compounds and methacrylate compounds.

[0046] Examples of maleimide compounds used as reactive diluents include, but are not limited to, maleimides; aliphatic hydrocarbon group-containing maleimides such as methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, and cyclohexyl maleimide; and aromatic ring-containing maleimides such as phenyl maleimide. These may be used individually or in combination of two or more.

[0047] The reactive diluent may be any one type, or two or more types may be used in combination.

[0048] When the curable composition of this embodiment contains a reactive diluent, the amount of the reactive diluent can be appropriately adjusted according to the desired viscosity, and is, for example, 0 to 50% by weight, or for example, 1 to 30% by weight, relative to the total weight of the curable composition. In one embodiment, the viscosity of the curable composition is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, even more preferably 20 Pa·s or less, and particularly preferably 10 Pa·s or less, at 25°C and a rotation speed of 5 rpm. Since dimer acid-modified N-substituted (meth)acrylamide has a lower viscosity compared to dimer acid-modified acrylamide, the curable composition has a low viscosity even without a reactive diluent, but further reduction in viscosity is possible with a reactive diluent.

[0049] The curable composition of this embodiment may contain a stabilizer, to the extent that it does not impair the effects of the present invention. The stabilizer is added to enhance the storage stability of the curable composition and to suppress the occurrence of unintended polymerization reactions caused by radicals or basic components. Typical examples of stabilizers include radical polymerization inhibitors and anionic polymerization inhibitors.

[0050] Known radical polymerization inhibitors can be used, including, but are not limited to, amine-based radical polymerization inhibitors such as N-nitroso-N-phenylhydroxylamine aluminum (NNAS) and phenothiazine; triphenylphosphine; phenol-based polymerization inhibitors such as p-methoxyphenol and 2,6-di-t-butyl-4-methylphenol; and hydroquinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, and di-t-butylhydroquinone. Known radical polymerization inhibitors disclosed in Japanese Patent Publication No. 2010-117545 and Japanese Patent Publication No. 2008-184514 can also be used. Any one radical polymerization inhibitor may be used, or two or more may be used in combination.

[0051] If a radical polymerization inhibitor is included, the content of the radical polymerization inhibitor is preferably 0.0001 to 5% by weight, and more preferably 0.001 to 3% by weight, relative to the total weight of the curable composition, from the viewpoint of pot life.

[0052] Known anionic polymerization inhibitors can be used, such as boric acid ester compounds and strong acids. Specific examples of anionic polymerization inhibitors include, but are not limited to, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, barbituric acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, and dichloroacetic acid. Furthermore, known anionic polymerization inhibitors disclosed in Japanese Patent Publication No. 2010-117545, Japanese Patent Publication No. 2008-184514, and Japanese Patent Publication No. 2017-171804 can also be used. Only one anionic polymerization inhibitor may be used, or two or more may be used in combination.

[0053] If an anionic polymerization inhibitor is included, the content of the anionic polymerization inhibitor is preferably 0.001 to 5% by weight, more preferably 0.01 to 3% by weight, based on the total weight of the curable composition.

[0054] The curable composition of this embodiment may contain other curable components other than the dimer acid-modified N-substituted (meth)acrylamide, to the extent that it does not impair the properties of the curable composition of this embodiment. Examples of other curable components include, but are not limited to, epoxy compounds (resins), (meth)acrylate compounds (resins), maleimide compounds (resins), acrylamide compounds (resins), vinyl ethers (resins), styrene derivatives, amine compounds (resins), oxetane compounds (resins), thiol compounds (resins), phenol compounds (resins), etc. In particular, by including a maleimide compound (resin) as another curable component in the curable composition, the maleimide compound can also function as a photoradical polymerization initiator, making it possible to photocur the composition without using other photoradical polymerization initiators. Bismaleimide having a dimer acid skeleton can be used as such a maleimide compound (resin).

[0055] The curable composition of this embodiment may, if desired, contain other additives, such as fillers, carbon black, titanium black, silane coupling agents, ion trapping agents, leveling agents, antioxidants, defoaming agents, viscosity modifiers, photosensitizers, or flame retardants, to the extent that they do not impair the properties of the curable composition of this embodiment, and as necessary. The type and amount of each additive are as per conventional methods. From the viewpoint of preventing reduced curing strength and adhesion, and preventing outgassing and bleeding, the curable composition of this embodiment is preferably substantially free of liquid components such as water, solvents, and ionic liquids (excluding liquid dimer acid-modified N-substituted (meth)acrylamide, other curable components, and reactive diluents). For example, the content of liquid components is preferably 3% by weight or less, and more preferably 1% by weight or less, relative to the total weight of the curable composition. Examples of solvents include common organic solvents in the field of curable compositions, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine oil, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

[0056] The method for producing the curable composition according to this embodiment is not particularly limited. The curable composition can be obtained, for example, by introducing each component simultaneously or separately into a suitable mixer, stirring and mixing them while melting them by heating if necessary, to obtain a homogeneous composition. The mixer is not particularly limited, but a Leikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill, etc., equipped with a stirring device and a heating device, can be used. These devices may also be used in appropriate combinations.

[0057] The curable composition of this embodiment can be a one-component curable composition contained in a single container, or a two-component (or multi-component) curable composition contained in two or more containers, depending on its application. In the case of a two-component (or multi-component) curable composition, it is conceivable to separate the dimer acid-modified N-substituted (meth)acrylamide from the radical polymerization initiator by placing the dimer acid-modified N-substituted (meth)acrylamide in an arbitrary container and the radical polymerization initiator in a separate container. Other optional components may be placed in each container as needed. An example of such an embodiment is a curable composition kit having a first container containing dimer acid-modified N-substituted (meth)acrylamide and other optional components as needed, and a second container containing the radical polymerization initiator and other optional components as needed.

[0058] The curable composition obtained in this manner is photocurable, thermocurable, or both photocurable and thermocurable, depending on the type of radical polymerization initiator it contains. Depending on the application, photocuring, thermocuring, or a combination of photocuring and thermocuring can be selected.

[0059] When a curable composition is photocured, the light used is, for example, ultraviolet (UV) light. In some embodiments, the curable composition may be photocured alone. In some embodiments, the curable composition may be photocured and then further heat-cured.

[0060] When curing a curable composition by heat, for example, it can be cured by heating at 60 to 200°C for 0.1 to 180 minutes. In some embodiments, the curable composition may be cured by heat alone. In some embodiments, heat curing and light irradiation may be used in combination.

[0061] The method of applying the curable composition of this embodiment is not particularly limited, and for example, it can be supplied to a desired part of a substrate or the like by known printing, dispensing, or coating methods. Examples of printing or dispensing methods include, but are not limited to, aerosol jet printing, inkjet printing (jet dispensing printing), screen printing, lithographic printing, cardboard printing, metallic printing, offset printing, gravure printing, flexographic printing, air dispensers, etc. Examples of coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, etc.

[0062] The curable composition of this embodiment can be used, for example, as an adhesive or sealant, or as a raw material, for fixing, joining, or protecting components constituting semiconductor devices or electronic components. In particular, compared to curable compositions containing bismaleimide having a dimer acid skeleton, the curable composition of this embodiment can provide a cured product with superior reliability because it has higher adhesive strength after photocuring and / or thermal curing, and a greater photocuring depth.

[0063] [Adhesive or Sealant] An adhesive or sealant according to one aspect of the present invention comprises the curable composition of the above aspect. This adhesive or sealant enables good bonding to general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.). The adhesive or sealant according to this aspect is preferably used for fixing, bonding, or protecting components constituting semiconductor devices or electronic components. Examples of semiconductor devices include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules and TOF sensor modules, other semiconductor modules, and integrated circuits.

[0064] The adhesive or sealant of this embodiment can be a one-component adhesive or sealant contained in a single container, or a two-component (or multi-component) adhesive or sealant contained in two or more containers, depending on its application. When using a two-component (or multi-component) adhesive or sealant, it is conceivable to separate the dimer acid-modified N-substituted (meth)acrylamide from the radical polymerization initiator by placing the dimer acid-modified N-substituted (meth)acrylamide in an arbitrary container and the radical polymerization initiator in a separate container. Other optional components may be placed in each container as needed. An example of such an embodiment is an adhesive or sealant kit having a first container containing dimer acid-modified N-substituted (meth)acrylamide and other optional components as needed, and a second container containing the radical polymerization initiator and other optional components as needed.

[0065] [Cured product of a curable composition or adhesive or sealant] A cured product according to one aspect of the present invention is a cured product obtained by curing the curable composition or adhesive or sealant according to the above aspect. This cured product is flexible and has excellent adhesion. In particular, compared to a cured product of a curable composition containing a bismaleimide having a dimer acid skeleton, it has higher adhesive strength after photocuring and / or thermal curing, and a higher photocuring depth, thus providing a highly reliable cured product.

[0066] [Semiconductor devices, electronic components] A semiconductor device or electronic component according to one aspect of the present invention includes a cured product according to the above aspect. Here, "semiconductor device" refers to all devices that can function by utilizing semiconductor properties, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules and TOF sensor modules, other semiconductor modules, and integrated circuits.

[0067] The present invention will be described in more detail below with reference to examples, reference examples, and comparative examples, but the present invention is not limited to these examples. In the following examples, reference examples, and comparative examples, parts and % refer to parts by weight and weight %, respectively, unless otherwise specified.

[0068] Example A: Production of Dimer Acid Modified N-Substituted (Meth)acrylamide The production of dimer acid modified N-substituted (meth)acrylamide was attempted as follows. For reference, dimer acid modified acrylamide was also produced.

[0069] Reference Manufacturing Example 1: Production of Dimer Acid Modified Acrylamide (1) Under an argon gas stream, 600 g of dimer amine 1 (Cargill Japan LLC product name "PRIAMINE 1075"), 6 L of cyclopentyl methyl ether (CPME), and 227.7 g of triethylamine were charged into a 10 L flask and cooled with ice. Acryloyl chloride (203.7 g) was added dropwise at an internal temperature of 15°C or below. After the addition was complete, the temperature was raised to room temperature. After 2 hours, the disappearance of the starting materials was confirmed by TLC and the reaction was considered complete. Distilled water (1 L), 1 M HCl (250 mL), and ethyl acetate (4 L) were added to the reaction solution. The organic layer was separated, and the remaining layer was extracted with ethyl acetate (2 L). The organic layers were combined, and saturated brine (1 L) and 1 M NaOH (300 mL) were added. The organic layer was separated, and the remaining layer was extracted with ethyl acetate (1.5 L). The obtained organic layer was collected and confirmed to be neutral, then dried over anhydrous sodium sulfate and filtered. Phenothiazine (65.9 mg (approximately 100 ppm)) was added to the organic layer, and the mixture was concentrated in an evaporator in a 35°C water bath to obtain 729 g of dimer acid-modified acrylamide composition (A'-1) containing approximately 89.9% by weight of dimer acid-modified acrylamide, approximately 10% by weight of CPME, and approximately 0.1% by weight of ethyl acetate. This composition is soluble in chloroform, and the CPME and ethyl acetate content was measured in deuterated chloroform. １ It was calculated from the integral value of the H NMR spectrum.

[0070] (2) Approximately 70 g of the dimer acid-modified acrylamide composition (A'-1) prepared in accordance with (1) above was further concentrated under high vacuum at 45°C to obtain 66 g of dimer acid-modified acrylamide composition (A'-2) containing approximately 5% by weight of CPME. This composition is soluble in chloroform, and the CPME content is １ It was calculated from the integral value of the H NMR spectrum.

[0071] (3) Approximately 14 g of the dimer acid modified acrylamide composition (A'-2) prepared in accordance with (2) above was placed in a beaker and dried in a vacuum dryer at 60°C for 8 hours to obtain 12.6 g of dimer acid modified acrylamide composition (A'-3). This composition is soluble in chloroform, １ No solvents such as CPME were detected by 1H NMR.

[0072] Production Example 1: Production of Dimer Acid Modified N-Methylacrylamide (NMeDAAA) A dimer acid acrylamide composition ((A'-1), net 9.54 g) synthesized in accordance with Reference Production Example 1 (1) was placed in a reaction vessel with a stirring bar, nitrogen purged, dissolved in 80 mL of anhydrous THF, and cooled on ice. 2.37 g of sodium hydride (50-72% in oil) was weighed into a separate flask, washed with hexane, suspended in 10 mL of anhydrous THF, and added to the reaction vessel. After returning to room temperature for 10 minutes, 4.20 g of iodomethane was added dropwise to the reaction vessel, and the reaction was carried out with stirring at room temperature for 4 hours. After confirming the disappearance of the starting materials, saturated ammonium chloride aqueous solution was added under ice cooling to quench the reaction. The mixture was diluted with ethyl acetate and extracted, and the organic layer was washed twice more with saturated sodium chloride aqueous solution. One mg of phenothiazine was added to the organic layer, dried with anhydrous sodium sulfate, filtered off the solid, concentrated the filtrate, and vacuum-dried to obtain the target product, dimer acid-modified N-methylacrylamide composition (A-1) (yield 9.75 g). This composition contains phenothiazine, which is a polymerization inhibitor, １ No solvents such as ethyl acetate were detected by 1H NMR. The content of the dimer acid derivative in the composition is 99% by weight or more.

[0073] Production Example 2: Production of Dimer Acid Modified N-Benzylacrylamide (NBnDAAA) Dimer acid acrylamide ((A'-1), net 4.50 g) synthesized in the manner of Reference Production Example 1 (1) was placed in a reaction vessel with a stirring bar and nitrogen purged, dissolved in 80 mL of anhydrous THF, and cooled on ice. 1.13 g of sodium hydride (50-72% in oil) was weighed into a separate flask, washed with hexane, and then suspended in 5 mL of anhydrous THF and added to the reaction vessel. After returning to room temperature for 10 minutes, 2.39 g of benzyl bromide was added dropwise to the reaction vessel and the reaction was carried out with stirring overnight at room temperature. After confirming the disappearance of the starting materials, saturated ammonium chloride aqueous solution was added and the mixture was quenched under ice cooling. The mixture was diluted with ethyl acetate and extracted, and the organic layer was washed twice more with saturated sodium chloride aqueous solution. The obtained organic layer was dried over anhydrous sodium sulfate, the solid was filtered off, 0.5 mg of phenothiazine was added and concentrated, and then vacuum-dried to obtain the target product, dimer acid-modified N-benzylacrylamide (A-2) (yield 4.66 g). This composition contains phenothiazine, which is a polymerization inhibitor, １ No solvents such as ethyl acetate were detected by 1H NMR. The content of the dimer acid derivative in the composition is 99% by weight or more.

[0074] [ １ [H NMR and Mass Spectrometry] The dimer acid-modified N-substituted (meth)acrylamide composition obtained in the above production example １ ¹H NMR and DART-MS (direct ionization mass spectrometry) analysis were performed. １ H NMR measurement example: Production example 1 (A-1): 1 H NMR (400 MHz, CDCl3) δ = 6.63-6.49 ppm (m, 2H), δ =6.39-6.26 ppm (m, 2H), δ = 5.72-5.61 ppm (m, 2H), δ = 3.41 ppm, 3.32 ppm (t, J = 8 Hz, 6 Hz, 4H), δ = 3.04 ppm, 2.99 ppm (s, 3H), δ = 1.39-0.75 ppm (m, 66H) Production example 2 (A-2): 1¹H NMR (400 MHz, CDCl3) δ = 7.51–7.06 ppm (m, 10 H), δ = 6.68–6.25 ppm (m, 4 H), δ = 5.81–5.57 ppm (m, 2 H), δ = 4.50 ppm (s, 4 H), δ = 3.42–3.14 (m, 4 H), δ = 1.46–0.60 ppm (m, 66 H) The conditions for DART-MS analysis are as follows.・Direct Analysis in Real Time-mass spectrometer Direct Analysis in Real Time system: DART (AMR Co. Ltd) Mass spectrometer: compact QTOF (Bruker Co. Ltd) ・Condition of DART Carrier Gas: Helium DART Temp.: 350°C ・Condition of mass spectrometry Ion Polarity: Positive Dry Heater temp.: 200 °C Charging Voltage: 2000 V Mass range(m / z): 50-3000

[0075] Figure 1 shows an example of the mass spectrum obtained by DART-MS analysis of the dimer acid-modified N-methylacrylamide obtained in Production Example 1. １ Based on 1H NMR and DART-MS analysis, it was estimated that the dimer acid-modified N-methylacrylamide obtained in Production Example 1 contained bis-N-methylacrylamide compounds with the following structures [1] to [5]. Structures [1] to [5] were identified from the corresponding peaks in the mass spectrum of Figure 1.

[0076] [Viscosity Measurement] The viscosity of the dimer acid-modified N-methylacrylamide composition (A-1) from Production Example 1, the dimer acid-modified acrylamide composition (A'-3) from the Reference Production Example, and the dimer acid-modified maleimide (A''-1) used in Example B described later was measured at 25°C and a rotation speed of 5 rpm using a digital viscometer DV-I Prime. The results are shown in Table 1.

[0077]

[0078] The viscosity of the dimer acid-modified acrylamide composition (A'-1) of Reference Production Example 1, which does not contain a solvent, is more than 50 times higher than that of the dimer acid-modified maleimide (A''-1). In contrast, the dimer acid-modified N-methylacrylamide composition (A-1) of Production Example 1 has a viscosity similar to that of the dimer acid-modified maleimide (A''-1).

[0079] Example B: Production and Performance Evaluation of Curable Compositions [Examples 1-8, Reference Example 1, Comparative Examples 1-6] Curable compositions were prepared by mixing predetermined amounts of each component according to the formulations shown in Tables 2-5. In Tables 2-5, the amount of each component is expressed in parts by weight. The components used in the Examples, Reference Examples and Comparative Examples are as follows.

[0080] • (A) Dimer acid-modified N-substituted (meth)acrylamide (A-1): The dimer acid-modified N-methylacrylamide composition (A-1) from Production Example 1 was used. The amounts of (A-1) listed in Tables 2 to 5 are for the composition including the polymerization inhibitor. (A-2): The dimer acid-modified N-benzylacrylamide composition (A-2) from Production Example 2 was used. The amounts of (A-2) listed in Tables 2 to 5 are for the composition including the polymerization inhibitor.

[0081] • (A') Dimer acid modified acrylamide (A'-2): The dimer acid modified acrylamide composition (A'-2) from Reference Production Example 1 was used. The amounts of (A'-2) listed in Tables 2 to 5 are the amounts of the composition including the medium and polymerization inhibitor.

[0082] • (A'') Dimer acid-modified maleimide (A''-1) 1,1'-((4-hexyl-3-octylcyclohexane-1,2-diyl)bis(octane-8,1-diyl))bis(1H-pyrrole-2,5-dione) dimer bismaleimide (product name: BMI-689, manufactured by DesignerMolecules)

[0083] • (B) Photoradical polymerization initiator (B-1): 1-Hydroxycyclohexylphenyl ketone (Product name: Omnirad 184, manufactured by IGM Resins)

[0084] • (C) Thermal radical polymerization initiator (C-1): 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (product name: Perocta-O, manufactured by NOF Corporation)

[0085] • (D) Reactive diluent (D-1): Dimethylol-tricyclodecanediaacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) (D-2) 1,4-cyclohexanedimethanol monoacrylate (product name: CHDMMA, manufactured by Mitsubishi Chemical Corporation)

[0086] In the examples, reference examples, and comparative examples, the properties of the curable compositions were measured as follows.

[0087] [UV Curing Depth Measurement] The curable compositions of Examples 1-7, Reference Example 1, and Comparative Examples 1-5 were degassed in a vacuum, coated to a thickness of 0.3 mm on an LCP (LAPEROS® E463i) plate, and then fixed by sandwiching them between LCP plates. UV irradiation dose of 2000 mJ / cm² was applied from the side. ２ Test specimens were prepared (n=6) by UV curing with an LED lamp (UV wavelength: 365 nm). The UV curing depth was determined by measuring the curing distance perpendicular to the UV-irradiated surface of the test specimen using a measuring microscope. The results are shown in Tables 2-4.

[0088] [Adhesion Strength of Cured Products] (1) The curable compositions obtained in Photocuring Examples 1-7, Reference Example 1, and Comparative Examples 1-5 were stencil-printed onto a nickel-plated substrate with a diameter of φ2 mm and a thickness of 125 μm. Test specimens were prepared by placing a 1.5 mm × 3 mm × 0.5 mm alumina chip on the printed resin composition with the 1.5 mm × 3 mm side facing downwards (n=10). Curing was performed using an Excelitas Technologies AC475 UV LED irradiation device from the alumina chip mounting surface (surface) with an integrated light intensity of 2000 mJ / cm². ２ (Measurements were taken using a UIT-250 (with a UVD-365 light receiver connected) manufactured by Ushio Inc.) The alumina chip on this substrate was punctured from the side with a MODEL-1605HTP strength tester manufactured by Aiko Engineering Co., Ltd., and the adhesive strength (shear strength) was calculated from the value obtained when the alumina chip peeled off. Test specimens were prepared using FR4 substrates and glass substrates using the same procedure, and the adhesive strength (shear strength) was measured. The results are shown in Tables 2 to 4. (2) The curable compositions obtained in Thermosetting Example 8 and Comparative Example 6 were stencil printed on a nickel-plated substrate with a diameter of φ2 mm and a thickness of 125 μm, and test specimens were prepared by placing a 1.5 mm × 3 mm × 0.5 mm alumina chip on the printed resin composition with the 1.5 mm × 3 mm side facing down (n = 10). Curing was performed by heating in a forced-air dryer at 120°C for 60 minutes. The alumina chips on this substrate were punctured from the side using an Aiko Engineering MODEL-1605HTP strength tester, and the adhesive strength (shear strength) was calculated from the value obtained when the alumina chips peeled off. The results are shown in Table 5.

[0089]

[0090] As can be seen from Table 2, the curable compositions containing dimer acid-modified N-substituted (meth)acrylamide of Examples 1 and 2 showed better photocuring depth and adhesive strength in photocuring compared to the curable composition containing dimer acid-modified maleimide of Comparative Example 1. Note that the adhesive strength of the curable composition of Example 2 was not measured in Table 2.

[0091]

[0092] In Examples 3-5 and Comparative Examples 2-4, the photocurability of curable compositions was confirmed when dimer acid-modified N-substituted (meth)acrylamide or dimer acid-modified maleimide was used in combination with a reactive diluent. As can be seen from Table 3, the curable compositions containing dimer acid-modified N-substituted (meth)acrylamide in Examples 3-5 showed improved photocuring depth when used in combination with a reactive diluent compared to the curable compositions containing dimer acid-modified maleimide in Comparative Examples 2-4.

[0093]

[0094] In Examples 6-7 and Comparative Example 5, the photocurability of curable compositions containing dimer acid-modified N-substituted (meth)acrylamide or dimer acid-modified maleimide and maleimide that can function as a photoradical polymerization initiator, without containing any photoradical polymerization initiator other than maleimide, was confirmed. As can be seen from Table 4, the curable compositions of Examples 6-7 containing dimer acid-modified N-substituted (meth)acrylamide and dimer acid-modified maleimide as a photoradical polymerization initiator showed improved photocuring depth compared to the curable composition of Comparative Example 5 containing only dimer acid-modified maleimide.

[0095]

[0096] In Example 8 and Comparative Example 6, the thermosetting properties when a thermal radical polymerization initiator was included were confirmed. As can be seen from Table 5, even in thermosetting, the curable composition containing dimer acid-modified N-substituted (meth)acrylamide in Example 8 obtained better adhesive strength compared to the curable composition containing dimer acid-modified maleimide in Comparative Example 6.

[0097] The disclosure of Japanese Patent Application No. 2024-172783 (filing date: October 1, 2024) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. The following equation (I): -NR １ C(O)CR ２ =CH ２ ...(I) (wherein, R １ R is an organic group with a formula weight of 110 or less. ２ A dimer acid-modified N-substituted (meth)acrylamide having an N-substituted (meth)acrylamide group represented by ) is hydrogen or methyl.

2. R １ The dimer acid-modified N-substituted (meth)acrylamide according to claim 1, wherein the organic group is selected from the group consisting of optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, optionally substituted acyl groups, optionally substituted cycloalkyl groups, optionally substituted cycloalkenyl groups, optionally substituted aliphatic heterocyclic groups, optionally substituted aryl groups, and optionally substituted heteroaryl groups, and has a formula weight of 110 or less.

3. A composition comprising a dimer acid-modified N-substituted (meth)acrylamide and a polymerization inhibitor according to claim 1 or 2, wherein the content of the dimer acid-modified N-substituted (meth)acrylamide in the composition is 99% by weight or more.

4. A curable composition comprising a dimer acid-modified N-substituted (meth)acrylamide and a radical polymerization initiator as described in claim 1 or 2.

5. The curable composition according to claim 4, wherein the radical polymerization initiator is a photoradical polymerization initiator.

6. The curable composition according to claim 4, wherein the radical polymerization initiator is a thermal radical polymerization initiator.

7. The curable composition according to any one of claims 4 to 6, further comprising a curable component other than the dimer acid-modified N-substituted (meth)acrylamide.

8. The curable composition according to any one of claims 4 to 7, wherein the dimer acid-modified N-substituted (meth)acrylamide and the radical polymerization initiator are contained in a single container.

9. The curable composition according to any one of claims 4 to 7, wherein the dimer acid-modified N-substituted (meth)acrylamide and the radical polymerization initiator are divided into two or more containers.

10. An adhesive or sealant comprising the curable composition according to any one of claims 4 to 9.

11. A cured product obtained by curing a curable composition according to any one of claims 4 to 9, or an adhesive or sealant according to claim 10.

12. A semiconductor device or electronic component comprising the cured product described in claim 11.

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