Classifications

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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
  • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
  • C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
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  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
  • C07C233/41—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a ring other than a six-membered aromatic ring
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
  • C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
  • C07C233/44—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a carbon atom of an unsaturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/56—Acrylamide; Methacrylamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F22/36—Amides or imides
  • C08F22/38—Amides
  • C08F22/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
  • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
  • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
  • C07C2602/14—All rings being cycloaliphatic
  • C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
  • C07C2602/28—Hydrogenated naphthalenes
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  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09K2200/0625—Polyacrylic esters or derivatives thereof
  • C09K2200/0627—Nitrogen-containing polymers, e.g. polyacrylamide

Definitions

• the present invention relates to a novel acrylamide, a composition containing the same, a curable composition, an adhesive or sealant containing the same, a cured product thereof, and a semiconductor device or electronic component containing the cured product.
• curable resin compositions are often used to assemble and mount electronic components, such as semiconductor chips, used in semiconductor devices, in order to maintain reliability, etc.
• a resin composition used for adhesives and sealants for such electronic components for example, a resin composition containing polymaleimide is known.
• Polymaleimides having two or more maleimide groups are known to be photocurable and heat curable by homopolymerization such as radical polymerization or ionic polymerization of the double bonds contained in the maleimide groups, addition reaction with hydrogen of aromatic amines, copolymerization with allylphenol, etc., to give cured products with excellent heat resistance, and to have good adhesive strength due to their high polarity.
• polymaleimides have a high crystallinity, a high melting point, and low solubility in organic solvents, which makes it difficult to melt or dissolve them to ensure moldability when used as a curable composition.
• there is a concern that many commercially available cured products of polymaleimides have a high water absorption rate and poor moisture resistance reliability.
• Patent Document 1 discloses an adhesive containing a bismaleimide compound that has a dimer acid skeleton or the like. Substances that primarily contain bismaleimides with such dimer acid skeletons are commercially available, such as BMI-689, BMI-1500, and BMI-1700 manufactured by Designer Molecules.
• Bismaleimides with a dimer acid skeleton have reactivity derived from the maleimide group, and can be polymerized by irradiation with light in the presence or absence of a photoradical generator, or by heating in the presence of a thermal radical generator.
• the dimer acid skeleton due to the dimer acid skeleton, they have the advantage of being able to produce a cured product that is moisture resistant and flexible (low elasticity).
• bismaleimides with a dimer acid skeleton have issues in that the curing depth and adhesive strength during photocuring are still insufficient.
• the present invention aims to provide a novel substance that can solve the problems associated with the above-mentioned bismaleimide having a dimer acid skeleton, a curable composition containing the substance that has excellent photocurability and adhesive strength, an adhesive or sealant, a cured product obtained by curing the substance, and a semiconductor device or electronic component that includes the cured product.
• Embodiments of the present invention include a novel acrylamide having the following aspects, a composition mainly containing the acrylamide, a curable composition containing the same, an adhesive or sealant, a cured product, and a semiconductor device or electronic component.
• a composition mainly containing the acrylamide a curable composition containing the same, an adhesive or sealant, a cured product, and a semiconductor device or electronic component.
• Dimer acid modified acrylamide (2) A composition comprising a dimer acid modified acrylamide and a medium, a polymerization inhibitor, or a combination thereof, A composition, wherein the content of dimer acid modified acrylamide in the composition is 83% by weight or more.
• a curable composition comprising a dimer acid-modified acrylamide and a radical polymerization initiator.
• a novel substance capable of solving the problems of bismaleimides having a dimer acid skeleton, a composition mainly containing the novel substance, a curable composition containing the novel substance and having excellent photocurability and adhesive strength, an adhesive or sealant, a cured product obtained by curing the novel substance, and a semiconductor device or electronic component containing the cured product.
• 1 is a 1 H NMR chart of the dimer acid-modified acrylamide composition (A-4) of Production Example 4.
• 1 is a 1 H NMR chart of the dimer acid-modified acrylamide composition (A-5) of Production Example 5.
• 1 is an example of a mass spectrum of the dimer acid-modified acrylamide composition (A-4) of Production Example 4.
• One embodiment of the present invention is a dimer acid modified acrylamide.
• Another embodiment of the present invention is a composition comprising a dimer acid modified acrylamide and a medium, a polymerization inhibitor, or a combination thereof, The content of the dimer acid modified acrylamide in the composition is 83% by weight or more.
• a liquid dimer acid modified acrylamide composition is provided that is substantially free of dimer acid modified acrylamide and by-products (e.g. hydrogen halide and its salts) produced during synthesis of the dimer acid modified acrylamide.
• dimer acid modified acrylamide or dimer acid modified acrylamide composition it becomes possible to prepare a curable composition that contains dimer acid modified acrylamide at an appropriate concentration and has excellent photocurability and adhesiveness.
• substantially free of by-products means that the amount of the by-products in the composition is less than 1% by weight.
• Dimer acid is a liquid fatty acid that contains as its main component a dibasic acid of C36 dicarboxylic acid produced by dimerization of C18 unsaturated fatty acid made from vegetable oils and fats, and may contain any amount of C18 unsaturated fatty acid (sometimes called C18 monomer acid), C54 trimer acid, other polymerized fatty acid, etc.
• C18 unsaturated fatty acid include oleic acid, linoleic acid, linolenic acid, etc.
• Examples of C36 dicarboxylic acid include acyclic, monocyclic, polycyclic, and aromatic ring compounds represented by the following structural formulas.
• the C36 dicarboxylic acid in the dimer acid may be a mixture containing these multiple C36 dicarboxylic acid compounds in any ratio depending on the vegetable raw material and the production method.
• dimer acid may contain any amount of C18 monomer acid, C54 trimer acid, other polymerized fatty acid, etc. depending on the production method, degree of purification, etc. In this specification, dimer acid may contain such monomer acid, trimer acid, other polymerized fatty acid, etc.
• dimer acid modified acrylamide refers to a substance that necessarily contains diacrylamide derived from a C36 dicarboxylic acid as the main component and may contain any amount of monoacrylamide derived from a C18 monomer acid, triacrylamide derived from a C54 trimer acid, or acrylamide derived from other polymerizable fatty acids (i.e., it may or may not contain them).
• hydrocarbon group derived from a dimer acid refers to a hydrocarbon group in which the terminal carboxyl group (--COOH) of a dimer acid is replaced with a methylene group (--CH 2 -), and is also referred to as a "dimer acid skeleton".
• Examples of diacrylamide in dimer acid modified acrylamide include, but are not limited to, the following: The formula: Acyclic type represented by the formula: The following formula: A monocyclic type represented by the formula: The formula: and polycyclic forms represented by the following formula: An aromatic ring type represented by the formula:
• the contents of diacrylamide, monoacrylamide, and triacrylamide contained in dimer acid modified acrylamide depend on the raw materials and the production and purification methods, and in one embodiment may be 75-100% by weight, 0-5% by weight, and 0-25% by weight, respectively, in another embodiment may be 90-100% by weight, 0-5% by weight, and 0-10% by weight, respectively, in another embodiment may be 95-100% by weight, 0-5% by weight, and 0-5% by weight, respectively, and in another embodiment may be 99-100% by weight, 0-1% by weight, and 0-1% by weight, respectively.
• the method for producing the dimer acid-modified acrylamide is not particularly limited, but may be, for example, a method comprising reacting a dimer diamine with an acrylic acid halide in a solvent in the presence or absence of a base.
• Dimer diamine is a substance in which the terminal carboxyl group (-COOH) of a dimer acid is replaced with an aminomethyl group (-CH 2 -NH 2 ), and may contain any amount of monoamine, triamine, etc. in addition to the diamine as the main component.
• the content of monoamine and triamine in dimer diamine depends on the raw material and the production and purification method.
• dimer diamine products include, but are not limited to, trade names "PRIAMINE 1071", “PRIAMINE 1073”, “PRIAMINE 1074”, and “PRIAMINE 1075” (all manufactured by Croda Japan Co., Ltd.).
• the trade name "PRIAMINE 1071” has a diamine content of about 75% by weight and a triamine content of about 25% by weight.
• the trade name "PRIAMINE 1075” has a diamine content of more than 99% by weight and a triamine content of less than 1% by weight.
• acrylic acid halide include acrylic acid chloride, acrylic acid bromide, and the like.
• the solvent may be any solvent that does not affect the reaction, and examples thereof include hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethylsulfoxide, 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.), and the like, and these can also be used in appropriate combination.
• hydrocarbons benzene, toluene,
• bases include, but are not limited to, triethylamine, pyridine, diisopropylethylamine, 2,6-lutidine, 4-dimethylaminopyridine, and the like.
• the reaction can be carried out at a temperature between 0°C and 50°C, preferably between 10°C and 30°C.
• the reaction is quenched.
• the dimer acid modified acrylamide produced has amphiphilicity, it is difficult to separate and purify it from the reaction mixture by the usual liquid separation extraction method.
• a gel that is insoluble in chloroform may be formed. This is thought to be due to the unintentional generation of radicals in a low oxygen state, which causes partial polymerization of the dimer acid modified acrylamide.
• the present inventors have succeeded in separating dimer acid-modified acrylamide at a high concentration from a reaction mixture, and have obtained one embodiment of the present invention, a composition comprising dimer acid-modified acrylamide and a medium, wherein the content of dimer acid-modified acrylamide in the composition is 83% by weight or more.
• the present inventors have succeeded in preparing a dimer acid modified acrylamide composition in which the amount of the medium is further reduced or which is substantially free of the medium by appropriately adding a polymerization inhibitor during concentration.
• another embodiment of the present invention is a composition containing a dimer acid modified acrylamide and a polymerization inhibitor, and the content of the dimer acid modified acrylamide in the composition is 83% by weight or more.
• the dimer acid modified acrylamide composition contains a medium and a polymerization inhibitor.
• the dimer acid modified acrylamide composition contains a polymerization inhibitor and is substantially free of the medium. In this specification, “substantially free of the medium” means that the amount of the medium in the composition is less than 0.5% by weight.
• the content of the dimer acid-modified acrylamide in the composition is, for example, 83% by weight or more and less than 100% by weight, for example, 85% by weight or more and less than 100% by weight, for example, 90 to 99% by weight, for example, 93 to 98% by weight.
• Methods for separating the dimer acid-modified acrylamide from the reaction mixture include, but are not limited to, the following methods.
• An acid such as hydrochloric acid and water are added to the reaction mixture, and inorganic substances and amines produced as by-products are removed by separation and washing.
• separation is difficult in a normal method because an emulsion is easily formed, but separation can be achieved by adding an inorganic salt such as table salt and an appropriate organic solvent such as ethyl acetate.
• the organic layer is washed with an alkaline aqueous solution such as sodium hydroxide, followed by saline.
• the organic layer is dried with a drying agent such as anhydrous sodium sulfate, filtered, and concentrated in the presence or absence of a polymerization inhibitor to obtain a composition containing 83% by weight or more of the dimer acid-modified acrylamide as the target product and a medium.
• the medium may be the solvent used in the reaction, the organic solvent used in the separation after the reaction, water, a reactive diluent (details will be described later), or a mixture thereof.
• the preferred viscosity of the medium is 1 Pa ⁇ s or less at 25°C.
• the composition obtained in (1) above can be further concentrated to obtain a composition containing a dimer acid-modified acrylamide in which the amount of the medium in the composition is further reduced or which is substantially free of the medium.
• a polymerization inhibitor can be used as appropriate.
• an amine-based polymerization inhibitor such as N-nitroso-N-phenylhydroxylamine aluminum (NNAS) or phenothiazine.
• NNAS N-nitroso-N-phenylhydroxylamine aluminum
• the content of the medium in the composition is preferably 1 to 17% by weight, more preferably 1 to 15% by weight, and even more preferably 2 to 8% by weight.
• the curable composition according to one embodiment of the present invention comprises: and a radical polymerization initiator. According to this embodiment, a curable composition having excellent photocurability and adhesive strength can be provided.
• the dimer acid modified acrylamide contained in the curable composition is the same as the dimer acid modified acrylamide in the above embodiment, so the description of the dimer acid modified acrylamide in the above embodiment also applies to this embodiment.
• the content of the dimer acid modified 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.
• the radical polymerization initiator includes a photoradical polymerization initiator and a thermal radical polymerization initiator.
• the radical polymerization initiator is a photoradical polymerization initiator.
• the radical polymerization initiator is a thermal radical polymerization initiator.
• the radical polymerization initiator includes a photoradical polymerization initiator and a thermal radical polymerization initiator.
• photoradical polymerization initiator promotes UV curing of the curable composition.
• photoradical polymerization initiator include, but are not limited to, alkylphenone compounds and acylphosphine oxide compounds.
• alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651, manufactured by IGM Resins B.V.); ⁇ -aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907, manufactured by IGM Resins B.V.); 1-hydroxycyclohexylphenyl ketone (commercially available as IGM Resins B.V.); Examples of the ⁇ -hydroxyalkylphenone include, but are not limited to, ⁇ -hydroxyalkylphenones such as Omnirad 184 manufactured by IGM Resins B.V.; 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 379EG manufactured by IGM Resins B.V.),
• acylphosphine oxide compounds include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819, manufactured by IGM Resins B.V.), etc.
• 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, benzil dimethyl ketal, benzo Phenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzo
• photoradical polymerization initiator various types of photoradical polymerization initiators may be used alone or in combination of two or more types.
• the content of the photoradical polymerization initiator is preferably 0.01 to 10% by weight, and more preferably 0.04 to 8% by weight, based on the total weight of the curable composition, from the viewpoint of the curing speed and pot life of the curable composition.
• thermal radical polymerization initiator various thermal radical polymerization initiators may be used alone or in combination of two or more.
• 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.
• the curable composition of the above embodiment may further include a reactive diluent, a solvent, or a combination thereof. This allows the viscosity of the curable composition to be adjusted, and the handling properties to be improved.
• the reactive diluent has a reactive group, which reacts with the curable component during curing and is incorporated into the molecule, thereby minimizing the deterioration of the performance of the curable composition.
• the reactive diluent there are no particular limitations on the reactive diluent, and any known material can be used, but from the viewpoint of reactivity with the acryloyl group of the dimer acid-modified acrylamide, it is preferable to use a (meth)acrylate compound or a maleimide compound having a viscosity of 1 Pa ⁇ s or less.
• the reactive diluent can also be added as a medium when extracting or concentrating the dimer acid-modified acrylamide.
• 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, iso Decyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzy
• maleimide compounds as reactive diluents include, but are not limited to, maleimides; aliphatic hydrocarbon group-containing maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; aromatic ring-containing maleimides such as phenylmaleimide; and the like. These may be used alone or in combination of two or more.
• any one of the reactive diluents may be used, or two or more of them may be used in combination.
• the content of the reactive diluent can be adjusted appropriately according to the desired viscosity, and is, for example, 0 to 99% by weight, e.g., 1 to 95% by weight, based on the total weight of the curable composition.
• the solvent may be a medium contained in the composition containing the dimer acid-modified acrylamide.
• it may be appropriately selected from organic solvents commonly used in the field of curable compositions, such as, but not limited to, 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.), alcohol
• the content of the solvent can be adjusted appropriately according to the desired viscosity, and is, for example, 0 to 60% by weight, for example, 0 to 15% by weight, for example, 0 to 6% by weight, relative to the total weight of the curable composition.
• the curable composition of this embodiment may contain a stabilizer to the extent that the effect of the present invention is not impaired.
• the stabilizer is added to increase the stability of the curable composition during storage and to suppress the occurrence of polymerization reactions due to unintended radicals or basic components.
• Typical stabilizers include radical polymerization inhibitors and anionic polymerization inhibitors.
• a known radical polymerization inhibitor can be used, and examples thereof include, 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 JP-A-2010-117545, JP-A-2008-184514, etc. can also be used. Any one of the radical polymerization inhibitors may be used, or two or more of them may be used in combination.
• the content of the radical polymerization inhibitor is preferably 0.0001 to 5% by weight, and more preferably 0.001 to 3% by weight, based on the total weight of the curable composition, from the viewpoint of pot life.
• anionic polymerization inhibitor such as a borate ester compound or a strong acid.
• 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.
• any known anionic polymerization inhibitor disclosed in JP-A-2010-117545, JP-A-2008-184514, JP-A-2017-171804, and the like can also be used. Any one of the anionic polymerization inhibitors may be used, or two or more of them may be used in combination.
• 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.
• the curable composition of this embodiment may contain other curable components other than the dimer acid modified acrylamide, as long as the characteristics of the curable composition of this embodiment are not impaired.
• 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), and phenolic compounds (resins).
• a maleimide compound (resin) in the curable composition as another curable component, it becomes possible to photocure the composition without using a photoradical polymerization initiator.
• a maleimide compound (resin) a bismaleimide having a dimer acid skeleton can be used.
• the curable composition of this embodiment may contain other additives, such as carbon black, titanium black, a silane coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a photosensitizer, or a flame retardant, as necessary, to the extent that the properties of the curable composition of this embodiment are not impaired.
• additives such as carbon black, titanium black, a silane coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a photosensitizer, or a flame retardant, as necessary, to the extent that the properties of the curable composition of this embodiment are not impaired.
• the type and amount of each additive are as per usual.
• the method for producing the curable composition of this embodiment is not particularly limited.
• the curable composition can be obtained, for example, by introducing each component into an appropriate mixer simultaneously or separately, and mixing and stirring while melting by heating if necessary, to form a homogeneous composition.
• This mixer is not particularly limited, but a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirring device and a heating device can be used. These devices may also be used in appropriate combination.
• the curable composition of this embodiment can be a one-part curable composition that is configured as being contained in a single container, or a two-part (or multi-part) curable composition that is configured as being divided into two or more containers, depending on the application, etc.
• a two-part (or multi-part) curable composition it is possible to separate the dimer acid-modified acrylamide from the radical polymerization initiator by placing the dimer acid-modified acrylamide in an arbitrary container and the radical polymerization initiator in a different container.
• Other optional components can be placed in each container as required.
• An example of such an embodiment is a curable composition kit having a first container containing the dimer acid-modified acrylamide and other optional components as required, and a second container containing the radical polymerization initiator and other optional components as required.
• the curable composition thus obtained is photocurable, heat curable, or photo- and heat curable, depending on the type of radical polymerization initiator contained. Depending on the application, photocuring, heat curing, or a combination of photocuring and heat curing can be selected.
• the light to be irradiated is, for example, ultraviolet (UV) light.
• the curable composition may be only photocured.
• the curable composition may be photocured and then further thermally cured.
• the curable composition When the curable composition is thermally cured, it can be cured, for example, by heat treatment at 60 to 200°C for 0.1 to 180 minutes. In some embodiments, the curable composition may be cured only by heat. In some embodiments, heat curing and light irradiation may be used in combination.
• the method of applying the curable composition of this embodiment is not particularly limited, and for example, it can be applied to a desired portion of a substrate or the like by a known printing method, dispensing method, or coating method.
• Printing or dispensing methods include, but are not limited to, aerosol jet printing, inkjet printing (jet dispense printing), screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, flexographic printing, air dispenser, and the like.
• Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, and the like.
• the curable composition of this embodiment can be used, for example, as an adhesive or sealant for fixing, joining, or protecting components that constitute a semiconductor device or electronic component, or as a raw material thereof.
• an adhesive or sealant for fixing, joining, or protecting components that constitute a semiconductor device or electronic component, or as a raw material thereof.
• An adhesive or sealant according to one embodiment of the present invention includes the curable composition according to the above embodiment.
• This adhesive or sealant enables good bonding to 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 embodiment is preferably used for fixing, adhering, or protecting components constituting a semiconductor device or electronic component.
• semiconductor devices include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and TOF sensor modules, other semiconductor modules, and integrated circuits.
• the adhesive or sealant of this embodiment can be a one-component adhesive or sealant that is configured as being contained in a single container, or a two-component (or multi-component) adhesive or sealant that is configured as being divided into two or more containers, depending on the application, etc.
• a two-component (or multi-component) adhesive or sealant it is possible to separate the dimer acid-modified acrylamide from the radical polymerization initiator by placing the dimer acid-modified acrylamide in an arbitrary container and the radical polymerization initiator in a different container.
• Other optional components can be placed in each container as required.
• An example of such an embodiment is an adhesive or sealant kit having a first container containing the dimer acid-modified acrylamide and other optional components as required, and a second container containing the radical polymerization initiator and other optional components as required.
• the cured product according to one embodiment of the present invention is a cured product obtained by curing the curable composition, adhesive, or sealant according to the above-mentioned embodiment.
• This cured product has flexibility and excellent adhesion.
• the cured product compared to a cured product of a curable composition containing a bismaleimide having a dimer acid skeleton, the cured product has higher adhesion strength and a higher UV curing depth, providing a cured product with excellent reliability.
• the semiconductor device or electronic component of one embodiment of the present invention includes the cured product of the above-mentioned embodiment.
• the semiconductor device refers to a device in general that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc.
• Examples of the semiconductor device or electronic component include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and TOF sensor modules, other semiconductor modules, integrated circuits, etc.
• Example A Preparation of dimer acid modified acrylamide Preparation of dimer acid modified acrylamide was attempted as follows.
• composition (A-1) containing a dimer acid-modified acrylamide. It was found from 1 H NMR that about 15% by weight of CPME and about 0.5% by weight of ethyl acetate remained at this stage. It is to be noted that this composition (A-1) does not contain a polymerization inhibitor. ⁇ Considerations> By devising an extraction solvent in comparison with Comparative Production Example 1, a dimer acid modified acrylamide composition containing about 15% by weight of a medium could be obtained.
• ethyl acetate which has a lower solubility of dimer acid modified acrylamide than CPME and has a higher affinity with water than CPME, is superior as an extraction solvent for dimer acid modified acrylamide.
• the detailed reason is unclear and is not limited thereto, but it is considered that the carbonyl group of ethyl acetate interacts with the NH group of acrylamide to prevent the formation of micelles by dimer acid modified acrylamide.
• Phenothiazine (65.9 mg (equivalent to about 100 ppm)) was added to the organic layer, and the mixture was concentrated with an evaporator in a water bath at 35° C. to obtain 729 g of a dimer acid-modified acrylamide composition (A-2) containing about 89.9 wt % of dimer acid-modified acrylamide, about 10 wt % of CPME, and about 0.1 wt % of ethyl acetate.
• This composition was soluble in chloroform, and the contents of CPME and ethyl acetate were calculated from the integrated values of 1 H NMR measured in deuterated chloroform.
• the reaction solution was cooled on ice, and distilled water (30 mL), 1 M HCl (7.5 mL), and ethyl acetate (90 mL) were added. The organic layer was separated, and the remaining layer was extracted with ethyl acetate (90 mL). The organic layers were combined, and saturated saline (30 mL) and 1 M NaOH (3 mL) were added. The organic layer was separated, and the remaining layer was extracted with ethyl acetate (45 mL). The obtained organic layers were combined, and after confirming that they were neutral, they were dried over sodium sulfate, filtered, and concentrated in an evaporator in a water bath at 45° C.
• a dimer acid-modified acrylamide composition (A-5) containing about 0.1 wt % ethyl acetate and 3.9 wt % CPME.
• This composition was soluble in chloroform, and the contents of ethyl acetate and CPME were calculated from the integrated value of 1 H NMR.
• the 1 H NMR chart of the dimer acid-modified acrylamide composition (A-5) is shown in FIG. 2.
• NNAS N-nitroso-N-phenylhydroxylamine aluminum
• ethyl acetate N-nitroso-N-phenylhydroxylamine aluminum (NNAS) (equivalent to 0.16 mg) diluted with ethyl acetate was added to 8.0 g of the dimer acid modified acrylamide composition (A-5) of Production Example 5 and mixed thoroughly, and the solvent was removed under high vacuum at 45° C. to obtain 8.0 g of a dimer acid modified acrylamide composition (A-6) containing about 20 ppm of NNAS, about 0.2 wt % of ethyl acetate and 3.3 wt % of CPME. This composition was soluble in chloroform, and the contents of ethyl acetate and CPME were calculated from the integrated values of 1 H NMR.
• Example B Preparation of curable composition and performance evaluation [Examples 1 to 13, Comparative Examples 1 to 10] Curable compositions were prepared by mixing the prescribed amounts of each component according to the formulations shown in Tables 2 to 4. In Tables 2 to 4, the amount of each component is expressed in parts by weight (unit: g). The components used in the examples and comparative examples are as follows.
• the amount of (A-3) shown in Table 1 is the amount as a composition including a medium and a polymerization inhibitor.
• the amount of (A-5) shown in Table 1 is the amount as a composition including a medium.
• the amount of (A-6) shown in Table 1 is the amount as a composition including the medium and the polymerization inhibitor.
• A' Dimer acid modified maleimide
• A'-1 Dimer bismaleimide mainly containing 1,1'-((4-hexyl-3-octylcyclohexane-1,2-diyl)bis(octane-8,1-diyl))bis(1H-pyrrole-2,5-dione) (Product name: BMI-689, manufactured by Designer Molecules)
• C Thermal radical polymerization initiator (C-1): 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (product name: Perocta O, manufactured by NOF Corporation)
• D Reactive Diluent
• D-1 Isobornyl Acrylate (Product Name: IBXA, manufactured by Kyoeisha Chemical Co., Ltd.)
• D-2) 1,4-Cyclohexanedimethanol monoacrylate (product name: CHDMMA, manufactured by Nippon Kasei Kogyo Co., Ltd.)
• D-3) Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.)
• the properties of the curable compositions were measured as follows.
• the alumina chip on this substrate was poked from the side with a MODEL-1605HTP type strength tester manufactured by Aiko Engineering Co., Ltd., and the adhesive strength (shear strength) was calculated from the numerical value when the alumina chip peeled off. The results are shown in Table 3.
• the curable composition containing the dimer acid-modified acrylamide of the example provided good cure depth and adhesive strength upon photocuring, compared to the curable composition containing the dimer acid-modified maleimide of the comparative example.
• the curable composition containing the dimer acid modified acrylamide of the example had better adhesive strength than the curable composition containing the dimer acid modified maleimide of the comparative example. This is thought to be because the NH group in the dimer acid modified acrylamide improved adhesion to the substrate.
• the UV cure depth did not decrease even when the amount of the photoradical polymerization initiator was reduced to 5 wt%, 3 wt%, or 1 wt% (Examples 9 to 11), but in the case of the curable composition containing dimer acid-modified maleimide, the UV cure depth was significantly reduced when the amount of the photoradical polymerization initiator added was reduced to 1% (Comparative Examples 7 to 9).
• maleimide is irradiated with light, radicals are generated via a [2+2] cycloaddition reaction, so curing is possible even when irradiated with UV light without adding a photoradical initiator. Even in this case, the UV curing depth could be improved by replacing part of the maleimide with a dimer acid-modified acrylamide (Examples 12 and 13, and Comparative Example 10).

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