Classifications

• • 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
  • C08F22/10—Esters
  • C08F22/12—Esters of phenols or saturated alcohols
  • C08F22/14—Esters having no free carboxylic acid groups
• • C—CHEMISTRY; METALLURGY
  • 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
  • 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
• • 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
  • C08F122/00—Homopolymers 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
  • C08F122/10—Esters
  • C08F122/12—Esters of phenols or saturated alcohols
  • C08F122/14—Esters having no free carboxylic acid groups
• • 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
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/22—Expanded, porous or hollow particles
  • C08K7/24—Expanded, porous or hollow particles inorganic
  • C08K7/26—Silicon- containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or 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, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/02—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/006—Additives being defined by their surface area
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/02—Inorganic compounds
  • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
  • C09K2200/0247—Silica

Definitions

• the present invention relates to a resin composition, a curable resin composition or kit containing the same, a cured product thereof, and an electronic component containing the cured product.
• a semiconductor device for example, an electronic device such as a smart phone is composed of various electronic modules. Components that constitute these electronic modules often use materials whose mechanical and electronic properties deteriorate due to heat. Therefore, it is preferable to assemble the electronic module and assemble and seal the electronic device under relatively low temperature conditions, for example, 100° C. or lower. Therefore, the adhesives and sealing materials used in the manufacture of the electronic devices and electronic modules are required to exhibit sufficient curability even under such low-temperature conditions (Patent Document 1).
• Patent Document 2 discloses a product that can be cured at a low temperature of 80° C. or less, preferably at room temperature, and that contains few components that volatilize during use (coating) or during curing, and is used in the manufacture of image sensor modules and electronic parts.
• a resin composition containing one or more 2-methylene-1,3-dicarbonyl compounds is disclosed as a resin composition suitable as a liquid adhesive.
• the curable resin composition used in such cases may need to exhibit a certain or higher viscosity (especially measured at a low shear rate).
• a curable resin composition in addition to suppressing displacement of members during bonding, dripping from the discharge device and contamination of other members (due to bleeding, flowing, etc.) are also suppressed. workability is improved.
• the pot life of the curable resin composition can be evaluated, for example, by gelation time.
• gelation means that the resin component (2-methylene-1,3-dicarbonyl compound in the present invention) is polymerized by a chemical reaction, and the resin composition loses fluidity. It is a phenomenon.
• the gelling time is the time from when the curable resin composition becomes ready to start curing to when the curable resin composition loses fluidity under predetermined conditions.
• curing and curing time refer to the phenomenon of solidification to the extent that it is possible to hold and adhere objects more firmly and strongly as polymerization progresses, regardless of whether or not a crosslinked structure is formed. It is that time which has a different definition than gelling and gelling time (pot life).
• an object of the present invention is to provide a resin composition containing a 2-methylene-1,3-dicarbonyl compound, which has improved workability.
• the present inventors have made intensive studies to solve the above problems, and found that a 2-methylene-1,3-dicarbonyl compound having a specific molecular weight and a fume having a specific average primary particle size and specific surface area
• the inventors have found that by including dosilica in the resin composition, the pot life (gelation time) and viscosity suitable for work are simultaneously imparted without causing variations in curability, and have arrived at the present invention. .
• the present invention includes, but is not limited to, the following inventions.
• (1) (A) the following formula (I): 2-methylene-1,3-dicarbonyl compound having at least one structural unit represented by and having a molecular weight of 230 to 1000; and (B) an average primary particle size of 1 nm to 50 nm, and A resin composition comprising fumed silica having a specific surface area of 50 m 2 /g to 250 m 2 /g.
• the gelling time (GT A ) to the ratio of the gelation time (GT) of the resin composition (here, in the measurement of the GT, the ratio of the mass of N,N-dimethylbenzylamine to the mass of the resin composition is the GT A (A) the ratio of the mass of N,N-dimethylbenzylamine to the mass of the 2-methylene-1,3-dicarbonyl compound in the measurement of is 1.1 to 3, described in (3) above. of the resin composition.
• the resin composition according to any one of (1) to (5) above which can be cured by the action of a basic compound as a curing agent or curing catalyst.
• the resin composition according to any one of (1) to (6) above further comprising a polymer compound.
• (A) The resin composition according to any one of (1) to (7) above, which does not substantially contain a Lewis acidic compound capable of coordinating to the carbonyl oxygen of the 2-methylene-1,3-dicarbonyl compound. .
• the resin composition according to any one of (1) to (8) above which is substantially inert to water in the atmosphere.
• a one-component curable resin composition comprising the resin composition according to any one of (1) to (9) above and a latent basic compound or photobase generator.
• a kit of a two-part mixed curable resin composition (A) The resin composition according to any one of (1) to (9) above; and (B) a curing agent or curing catalyst containing a basic compound. (12) The resin composition according to any one of (1) to (9) above, the one-component curable resin composition according to (10) above, or the kit according to (11) above, which is used for the manufacture of electronic parts. (13) A cured product obtained by curing the resin composition according to any one of (1) to (9) above, the one-part curable resin composition according to (10) above, or the kit according to (11) above. . (4) An electronic component comprising the cured product according to (13) above.
• a resin composition containing a 2-methylene-1,3-dicarbonyl compound, a one-component curable resin composition, which has a pot life (gelation time) and viscosity suitable for work And a kit of a two-component mixed type curable resin composition can be obtained.
• the resin composition, the one-component curable resin composition, and the two-component mixed curable resin composition kit of the present invention are useful for the production of various electronic components.
• the present invention relates to resin compositions.
• This composition (A) the following formula (I): 2-methylene-1,3-dicarbonyl compound having at least one structural unit represented by and having a molecular weight of 230 to 1000; and (B) an average primary particle size of 1 nm to 50 nm, and It contains fumed silica having a specific surface area of 50 m 2 /g to 250 m 2 /g.
• Components contained in the resin composition of the present invention are described below.
• the resin composition of the present invention contains (A) a 2-methylene-1,3-dicarbonyl compound.
• (A) 2-methylene-1,3-dicarbonyl compound has the following formula (I): is a compound having at least one structural unit represented by (A) 2-methylene-1,3-dicarbonyl compound contains one or more structural units of formula (I) above.
• (A) the 2-methylene-1,3-dicarbonyl compound contains 2 to 6, preferably 2 structural units of formula (I) above.
• the structural unit of formula (I) consists of a vinyl group having two carbonyl groups covalently bonded to one ⁇ -bonded carbon and a vinyl group having no substituent covalently bonded to the other ⁇ -bonded carbon.
• the ⁇ -bonded carbon in the vinyl group to which the carbonyl group is not bonded is susceptible to attack by a nucleophilic reagent (that is, the vinyl group is activated ing).
• This provides (A) 2-methylene-1,3-dicarbonyl compound with high polymerizability.
• 2-methylene-1,3-dicarbonyl compound contains the structural unit of the formula (I), so in the presence of a polymerization initiator, typically a basic compound, Polymerization occurs.
• the 2-methylene-1,3-dicarbonyl compound has a molecular weight of 230 to 1000, preferably 230 to 800, more preferably 240 to 800, still more preferably 240 to 700; Especially preferably 250-700, most preferably 250-550.
• each 2-methylene-dicarbonyl compound can be determined, for example, by a reversed-phase high-performance liquid chromatography (reversed-phase HPLC) technique, using an ODS column as a column, a mass spectrometer (MS) and a PDA (detection wavelength: 190-800 nm) or by calibration using ELSD.
• a reversed-phase high-performance liquid chromatography reversed-phase HPLC
• MS mass spectrometer
• PDA detection wavelength: 190-800 nm
• (A) 2-methylene-1,3-dicarbonyl compound may contain a polyfunctional component.
• Polyfunctional means that the 2-methylene-1,3-dicarbonyl compound contains two or more structural units of formula (I) above.
• the number of structural units of formula (I) contained in the 2-methylene-1,3-dicarbonyl compound is referred to as the "functional number" of the 2-methylene-1,3-dicarbonyl compound.
• those with one functional group are “monofunctional”, those with two functional groups are “difunctional”, and those with three functional groups are “trifunctional”. call. Since the cured product obtained using the (A) 2-methylene-1,3-dicarbonyl compound containing a polyfunctional component is crosslinked, the physical properties of the cured product, such as heat resistance and mechanical properties at high temperatures, are improved. do.
• the cured product forms a network-like crosslinked structure, so that it flows even at high temperatures, especially at temperatures above the glass transition temperature. maintains a constant storage modulus.
• the storage modulus of the cured product at high temperatures can be evaluated, for example, by dynamic viscoelasticity measurement (DMA).
• DMA dynamic viscoelasticity measurement
• a cured product having a crosslinked structure is evaluated by DMA, a region called a plateau in which the change in storage elastic modulus with temperature is relatively small is observed over a wide range in the temperature range above the glass transition temperature.
• the storage modulus in the plateau region is evaluated as the crosslink density, ie, the amount related to the polyfunctional component content in (A) the 2-methylene-1,3-dicarbonyl compound.
• the mass ratio of (A) 2-methylene-1,3-dicarbonyl compound is preferably 0.05 to 0.99, more preferably 0.10 to 0.98, more preferably 0.20 to 0.97, particularly preferably 0.50 to 0.95.
• the 2-methylene-1,3-dicarbonyl compound has the following formula (II): (In the formula, X 1 and X 2 each independently represent a single bond, O or NR 3 (wherein R 3 represents hydrogen or a monovalent hydrocarbon group), R 1 and R 2 each independently represent hydrogen, a monovalent hydrocarbon group, or the following formula (III): (In the formula, X 3 and X 4 each independently represent a single bond, O or NR 5 (wherein R 5 represents hydrogen or a monovalent hydrocarbon group), W represents a spacer, R 4 represents hydrogen or a monovalent hydrocarbon group)) is represented by
• the 2-methylene-1,3-dicarbonyl compound has the following formula (IV): (In the formula, R 1 and R 2 are each independently hydrogen, a monovalent hydrocarbon group or the following formula (V): (In the formula, W represents a spacer, R 4 represents hydrogen or a monovalent hydrocarbon group)) is represented by
• the 2-methylene-1,3-dicarbonyl compound has the following formula (VI):
• R 11 has the following formula (VII): represents a 1,1-dicarbonylethylene unit represented by each R 12 independently represents a spacer, R 13 and R 14 each independently represent hydrogen or a monovalent hydrocarbon group, X 11 and each of X 12 and X 13 each independently represents a single bond, O or NR 15 (wherein R 15 represents hydrogen or a monovalent hydrocarbon group); each m independently represents 0 or 1, n represents an integer from 1 to 20) is a dicarbonylethylene derivative represented by
• a monovalent hydrocarbon group refers to a group produced by removing one hydrogen atom from a carbon atom of a hydrocarbon.
• the monovalent hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, alkyl-substituted cycloalkyl groups, aryl groups, aralkyl groups and alkaryl groups, some of which include N, Heteroatoms such as O, S, P and Si may be included.
• a monovalent hydrocarbon group partially containing a hetero atom may have, for example, a polyether structure or a polyester structure.
• the monovalent hydrocarbon groups are alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, allyl, alkoxy, alkylthio, hydroxyl, nitro, amido, azide, cyano, acyloxy, carboxy, sulfoxy, acryloxy, siloxy, epoxy, respectively. , or may be substituted with an ester.
• the monovalent hydrocarbon group is preferably an alkyl group substituted with an alkyl group, a cycloalkyl group, an aryl group or a cycloalkyl group, more preferably an alkyl group, a cycloalkyl group or a cycloalkyl group. is an alkyl group substituted with
• alkyl group The number of carbon atoms in the alkyl group, alkenyl group, and alkynyl group (hereinafter collectively referred to as "alkyl group, etc.") is not particularly limited.
• the number of carbon atoms in the alkyl group is generally 1-18, preferably 1-16, more preferably 2-12, more preferably 3-10, particularly preferably 4-8.
• the alkenyl group and alkynyl group usually have 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, more preferably 3 to 7 carbon atoms, and particularly preferably 3 to 6 carbon atoms.
• the carbon number of the alkyl group or the like is usually 5-16, preferably 5-14, more preferably 6-12, more preferably 6-10.
• the number of carbon atoms in the alkyl group or the like can be specified, for example, by the above reversed-phase HPLC or nuclear magnetic resonance method (NMR method).
• the structure of the alkyl group, etc. is not particularly limited.
• the alkyl group or the like may be linear or may have a side chain.
• the alkyl group or the like may have a chain structure or a cyclic structure (a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group).
• the alkyl group or the like may have one or more other substituents.
• the alkyl group or the like may have a substituent containing atoms other than carbon atoms and hydrogen atoms.
• the alkyl group and the like may contain one or more atoms other than carbon atoms and hydrogen atoms in the chain structure or the cyclic structure.
• Atoms other than carbon atoms and hydrogen atoms include, for example, one or more of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.
• alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, Examples include isopentyl, neopentyl, hexyl, heptyl, octyl, and 2-ethylhexyl groups.
• cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a 2-methylcyclohexyl group.
• alkenyl groups examples include vinyl groups, allyl groups, and isopropenyl groups.
• Specific examples of the cycloalkenyl group include a cyclohexenyl group.
• R 1 or R 2 is particularly preferably an alkyl group having 2 to 8 carbon atoms, a cycloalkyl group, an alkyl-substituted cycloalkyl group, an aryl group, an aralkyl group or an alkaryl group.
• a spacer refers to a divalent hydrocarbon group, more specifically a cyclic, linear or branched substituted or unsubstituted alkylene group.
• the number of carbon atoms in the alkylene group is not particularly limited.
• the alkylene group usually has 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and still more preferably 4 to 8 carbon atoms.
• the alkylene group may optionally include groups containing heteroatoms selected from N, O, S, P, and Si.
• the alkylene group may have an unsaturated bond.
• the spacer is an unsubstituted alkylene group of 4-8 carbon atoms.
• the spacer is a linear substituted or unsubstituted alkylene group, more preferably represented by the formula —(CH 2 ) n —, where n is an integer from 2 to 10, preferably from 4 to 8.
• Specific examples of the divalent hydrocarbon group as the spacer include, but are not limited to, a 1,4-n-butylene group and a 1,4-cyclohexylene dimethylene group.
• the terminal monovalent hydrocarbon group preferably has 6 or less carbon atoms. That is, when the 2-methylene-1,3-dicarbonyl compound is represented by the formula (II) or (IV), R 4 in the formula (III) or (V) is an alkyl group having 1 to 6 carbon atoms However, when one of R 1 and R 2 is represented by formula (III) or formula (V), the other of R 1 and R 2 is an alkyl group having 1 to 6 carbon atoms Preferably.
• both R 1 and R 2 may be represented by formula (III) or formula (V), but preferably one of R 1 and R 2 is represented by the above formula (III) or formula (V).
• the 2-methylene-1,3-dicarbonyl compound is represented by formula (IV) above.
• one of R 1 and R 2 in formula (IV) is an ethyl group, n-hexyl group, or cyclohexyl group, and the other is represented by formula (V).
• W is either a 1,4-n-butylene group or a 1,4-cyclohexylene dimethylene group
• R 4 is an ethyl group, an n-hexyl group, or a cyclohexyl group.
• R 1 and R 2 in the above formula (IV) are represented by the above formula (V), and W is a 1,4-n-butylene group or 1,4-cyclohexylene dimethylene and R 4 is either an ethyl group, an n-hexyl group or a cyclohexyl group.
• 2-methylene-1,3-dicarbonyl compounds can be synthesized by methods disclosed in published patent publications such as WO2012/054616, WO2012/054633 and WO2016/040261.
• both ends of the structural unit represented by the formula (I) contained in the 2-methylene-1,3-dicarbonyl compound are bound to oxygen atoms, it is disclosed in Japanese Patent Publication No. 2015-518503.
• the 2-methylene-1,3-dicarbonyl compound produced in this manner is represented by R 1 and R 2 in formula (II) or formula (IV), formula (III) or formula (V).
• R 4 in and R 14 and R 13 in formula (VI) above may contain a hydroxy group.
• a polyfunctional component that is, a 2-methylene-1,3-dicarbonyl compound having two or more structural units of formula (I)
• JP-A-2015-517973 JP-A-2015-517973. It can be synthesized by the disclosed method.
• Examples of compounds preferred as (A) the 2-methylene-1,3-dicarbonyl compound include dipentylmethylenemalonate, dihexylmethylenemalonate, dicyclohexylmethylenemalonate, ethyloctylmethylenemalonate, and propylhexylmethylenemalonate. 2-ethylhexyl-ethylmethylenemalonate, ethylphenyl-ethylmethylenemalonate, and the like. These are preferred due to their low volatility and high reactivity. Dihexylmethylenemalonate and dicyclohexylmethylenemalonate are particularly preferred from the standpoint of handleability.
• 2-methylene-1,3-dicarbonyl compound (A) one of the above-described 2-methylene-1,3-dicarbonyl compounds may be used, or two or more thereof may be used in combination. .
• the resin composition of the present invention contains (B) fumed silica having an average primary particle size of 1 nm to 50 nm and a specific surface area of 50 m 2 /g to 250 m 2 /g.
• the resin composition containing (A) the 2-methylene-1,3-dicarbonyl compound is simultaneously imparted with a pot life (gelation time) and viscosity suitable for work without causing variations in curability. be done.
• Fumed silica is particulate synthetic amorphous silica obtained by hydrolyzing halogenated silane such as silicon tetrachloride in an oxyhydrogen flame (dry method).
• Fumed silica includes aggregates in which primary particles (average primary particle size of about 1 to 200 nm) are fused by relatively strong interactions. Some of these aggregates are further fused through relatively weak interactions to form agglomerates. The aggregated particles are easily de-agglomerated by dispersing them in an appropriate medium, but it is difficult to de-aggregate the aggregated particles to primary particles by ordinary methods. It is
• the average primary particle size of (B) fumed silica is 1 nm to 50 nm.
• the average primary particle size of (B) fumed silica is preferably 1 to 40 nm, more preferably 1 to 20 nm.
• the average primary particle size of (B) fumed silica is preferably 3 to 50 nm, more preferably 5 to 30 nm. .
• the average primary particle size of (B) fumed silica is preferably 5 to 20 nm, more preferably 5 to 15 nm.
• the gelling time is the time from when the curable resin composition is ready to start curing to when the curable resin composition loses fluidity under predetermined conditions. It's time.
• the curing time refers to the time required for solidification to such an extent that an object can be held and adhered more firmly and strongly as polymerization progresses, regardless of whether or not a crosslinked structure is formed. be.
• (B) the average primary particle size of fumed silica is obtained by analyzing a transmission electron micrograph taken of a sample of (B) fumed silica using image processing software. Then, the size of all or part of the grains in the photograph is measured by digitizing and statistically processing.
• the specific surface area of (B) fumed silica is 50 m 2 /g to 250 m 2 /g. In certain embodiments, the specific surface area of (B) fumed silica is preferably 50 m 2 /g to 240 m 2 /g from the viewpoint of ensuring a longer pot life (gelation time). In one aspect, from the viewpoint of shortening the curing time, the specific surface area of (B) fumed silica is preferably 80 to 250 m 2 /g, more preferably 100 to 250 m 2 /g, and still more preferably 110 to 250 m 2 /g. In this specification, the specific surface area of (B) fumed silica is measured by the BET method unless otherwise specified.
• the surface of fumed silica may be hydrophobized with a surface treatment agent.
• a surface treatment agent e.g., silicone oils (eg, polydimethylsiloxane), silane coupling agents (eg, n-octyltrialkoxysilane), silylating agents (eg, hexamethyldisilazane and dimethyldichlorosilane), and the like. can.
• the surface treatment agent is preferably silicone oil, a silane coupling agent, or a silylating agent, and more preferably silicone oil, hexamethyldisilazane, or dimethyldichlorosilane.
• the surface treatment agents used for hydrophobization may be used alone or in combination of two or more.
• a plurality of fumed silicas whose surfaces have been hydrophobized with different surface treatment agents may be used in combination.
• the content of (B) fumed silica in the resin composition of the present invention is not particularly limited.
• the content of (B) fumed silica per 1 part by mass of the resin composition of the present invention is preferably 0.01 to 0.3 parts by mass, more preferably 0.02 to 0.24 parts by mass. , and particularly preferably 0.03 to 0.19 parts by mass.
• the resin composition of the present invention may optionally contain the following components in addition to (A) the 2-methylene-1,3-dicarbonyl compound and (B) fumed silica.
• the resin composition of the present invention may further contain an inorganic filler other than (B) fumed silica.
• Inorganic fillers include silica produced by methods other than the dry process such as the melting method, deflagration method (VMC (Vaporized Metal Combustion) method), and sol-gel method, and metal oxides such as calcium carbonate, alumina, and zinc oxide. , nickel, copper, silver and other metals, glass beads, bentonite, acetylene black, ketjen black and the like.
• the inorganic filler may be surface-treated with a silane coupling agent or the like. When using a surface-treated inorganic filler, an effect of preventing aggregation of the inorganic filler is expected.
• An inorganic filler may be used independently and may use 2 or more types together.
• the average particle diameter of the inorganic filler (the average maximum diameter if not spherical) is not particularly limited, but it is preferably 0.005 to 50 ⁇ m in order to uniformly disperse the filler in the resin composition. In addition, it is preferable because of excellent injectability when the resin composition is used as a liquid sealing material such as an adhesive or an underfill.
• the average particle size of the inorganic filler is measured with a laser diffraction scattering particle size distribution analyzer or a dynamic light scattering Nanotrack particle size analyzer.
• the inorganic filler may be either insulating or conductive.
• the content of the inorganic filler is preferably 0 to 95 parts by mass, more preferably 0 to 95 parts by mass with respect to the total 100 parts by mass of all components of the resin composition when the inorganic filler is insulating. 85 parts by mass, more preferably 0 to 50 parts by mass.
• the content of the inorganic filler is It is preferably 0 to 50 parts by mass with respect to a total of 100 parts by mass of all components.
• the content of the inorganic filler is preferably 10 to 95 parts by mass with respect to the total 100 parts by mass of all components of the resin composition, from the viewpoint of reducing the linear expansion coefficient of the resin composition. be.
• the content of the inorganic filler is 50 to 95 parts by mass with respect to a total of 100 parts by mass of all components of the resin composition so that it can be used as a conductive paste. is preferable from the viewpoint of electrical conductivity.
• the resin composition of the present invention may further contain a stabilizer.
• Stabilizers are used to increase the storage stability of the resin composition, and are added to suppress the occurrence of polymerization reactions caused by unintended radicals and basic components.
• a 2-methylene-1,3-dicarbonyl compound may generate a radical by itself with a low probability, and an unintended radical polymerization reaction may occur with the radical as a starting point.
• 2-methylene-1,3-dicarbonyl compounds may undergo an anionic polymerization reaction when mixed with a very small amount of a basic component. By adding a stabilizer, it is possible to suppress the occurrence of such unintended polymerization reactions due to radicals and basic components.
• a known stabilizer can be used, and for example, a strong acid or a radical scavenger can be used.
• specific stabilizers include trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, Mention may be made of 4-methoxyphenol, and hydroquinone.
• preferred stabilizers are at least one selected from maleic acid, methanesulfonic acid, N-nitroso-N-phenylhydroxylamine aluminum and 4-methoxyphenol.
• the known stabilizer disclosed in JP-A-2010-117545 and JP-A-2008-184514 can also be used.
• a stabilizer may be used independently and may use 2 or more types together.
• the resin composition of the present invention may further contain a surface treatment agent, if desired.
• the surface treatment agent is not particularly limited, but typically a coupling agent can be used.
• the coupling agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds with the inorganic material, and the other of which chemically bonds with the organic material. It is a functional group.
• coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, titanium coupling agents, and the like. Coupling agents may be used alone or in combination of two or more.
• Examples of functional groups that the coupling agent has and chemically bond with organic materials include vinyl groups, epoxy groups, styryl groups, methacrylic groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, sulfide groups, and isocyanates. and the like.
• Pigment may further contain a pigment, if desired.
• a pigment By including a pigment, the chromaticity of the resin composition of the present invention can be adjusted.
• the pigment is not particularly limited, for example, carbon black, titanium black such as titanium nitride, black organic pigment, mixed color organic pigment, inorganic pigment, and the like can be used.
• black organic pigments include perylene black and aniline black.
• mixed-color organic pigments include those obtained by mixing at least two kinds of pigments selected from red, blue, green, purple, yellow, magenta, cyan, etc. to produce a pseudo-black color.
• inorganic pigments include fine particles of graphite, metals and their oxides, composite oxides, sulfides, nitrides, and the like.
• this metal include titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and the like.
• a pigment may be used independently and may use 2 or more types together.
• the pigment is preferably carbon black or titanium black.
• the resin composition of the present invention may further contain a plasticizer, if desired. Any known plasticizer can be blended as the plasticizer.
• the plasticizer can improve moldability and adjust the glass transition temperature.
• a plasticizer that has good compatibility and does not easily bleed can be used.
• plasticizers include phthalates such as di-n-butyl phthalate, di-n-octyl phthalate, bis(2-ethylhexyl) phthalate, di-n-decyl phthalate, and diisodecyl phthalate; bis(2-ethylhexyl ) adipates such as adipate and di-n-octyl adipate; sebacates such as bis(2-ethylhexyl) sebacate and di-n-butyl sebacate; azelates such as bis(2-ethylhexyl) azelate; Paraffins such as chlorinated paraffin; Glycols such as polypropylene glycol; Epoxy-modified vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; Phosphate esters such as trioctyl phosphate and triphenyl phosphate; phosphites; ester
• the resin composition of the present invention may further contain a polymer compound, if desired.
• the resin composition of the present invention further contains a polymer compound.
• a polymer compound is usually used for the purpose of adjusting the viscosity of the resin composition.
• the polymer compound may be dissolved or dispersed as a particulate solid, but is preferably dissolved.
• the polymer compound When the polymer compound is dissolved in the resin composition of the present invention, the polymer compound preferably has a weight average molecular weight of 10,000 to 1,000,000. From the viewpoint of this solubility, the polymer compound is preferably a (meth)acrylate polymer.
• the term "(meth)acrylate polymer” is a generic term for "acrylate polymer” and "methacrylate polymer”.
• Acrylate polymers are polymers obtained by polymerizing one or more alkyl acrylates (alkyl esters of acrylic acid), and methacrylate polymers are polymers obtained by polymerizing one or more alkyl methacrylates (alkyl esters of methacrylic acid). is a polymer.
• (Meth)acrylate polymers also include copolymers obtained by copolymerizing alkyl acrylates and alkyl methacrylates.
• the average primary particle size of the particulate solid is preferably 100 ⁇ m or less.
• the particulate solid may be formed of crystals of a polymer compound, or may be formed of an amorphous polymer compound.
• the content of the polymer compound is preferably 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of all components of the resin composition, More preferably, it is 1 to 10 parts by mass.
• the resin composition of the present invention further contains components other than the above components, such as flame retardants, ion trapping agents, antifoaming agents, leveling agents, foam breaking agents, solvents, etc., to the extent that the effects of the present invention are not impaired. You may It is preferable not to contain an organic solvent when considering the influence on the environment.
• the resin composition of the present invention contains the above components as necessary.
• the resin composition of the present invention can be prepared by mixing these components.
• a known device can be used for mixing.
• it can be mixed by a known device such as a Henschel mixer or a roll mill. These components may be mixed at the same time, or a part may be mixed first and the rest may be mixed later.
• the resin composition of the present invention may have various physical and/or chemical properties as necessary, taking into account workability in assembling and mounting electronic components used in semiconductor devices.
• the resin composition of the present invention preferably has a viscosity of 100 to 100,000 mPa s, more preferably 200 to 80,000 mPa s, measured at 1 rpm using an E-type viscometer. s, more preferably 500 to 50,000 mPa ⁇ s, particularly preferably 1,000 to 10,000 mPa ⁇ s.
• the viscosity of the resin composition (measured at a low shear rate) is within the above range, misalignment during assembly/installation, dripping from the discharge device, and contamination of other members (due to bleeding, flowing, etc.) can be prevented. It can be suppressed, and workability is improved.
• a curable resin composition can be produced by combining the resin composition of the present invention with a curing agent or curing catalyst containing a basic compound.
• the basic compound is expected to contribute to the polymerization initiation reaction when the curable resin composition is cured by Michael addition reaction.
• the basic compounds used in the present invention may be used alone or in combination of two or more.
• the present invention also provides a curable resin composition, particularly a one-component curable resin composition, comprising the resin composition of the present invention and one or more basic compounds.
• the method of bringing the resin composition of the present invention into contact with the basic compound is not particularly limited. Examples of such methods include a method of mixing the resin composition of the present invention with a basic compound, and a method of applying the resin composition of the present invention onto a basic compound previously applied to the surface of an adherend. and a method of applying the resin composition of the present invention to the surface of a solid adherend having basic sites on its surface.
• the basic compound used in the present invention is not particularly limited as long as it is a compound exhibiting sufficient basicity to act as a curing agent or a curing catalyst for the resin composition of the present invention, but typically an organic base , inorganic bases, or organometallic materials.
• organic bases include amine compounds described later.
• inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; lithium carbonate, potassium carbonate, sodium carbonate and the like. alkali or alkaline earth metal carbonates; metal hydrogencarbonates such as potassium hydrogencarbonate and sodium hydrogencarbonate; and the like.
• Organometallic materials include organic alkali metal compounds such as butyllithium, t-butyllithium and phenyllithium, and organic copper reagents prepared therefrom; organic alkaline earth metal compounds such as methylmagnesium bromide, dimethylmagnesium and phenylmagnesium chloride. compounds and organocopper reagents prepared therefrom; and alkoxides such as sodium methoxide, t-butyl methoxide; carboxylates such as sodium benzoate;
• the basic compound used in the present invention preferably does not contain alkali metals, alkaline earth metals, transition metal elements, or halogen elements.
• the basic compounds used in the present invention are non-ionic. Basic compounds are broadly classified into ionic and nonionic compounds. In particular, when the basic compound is mixed with the resin composition of the present invention, the basic compound may be nonionic. preferable.
• the basic compound used in the present invention is preferably an organic base, more preferably an amine compound.
• the amine compound is an organic compound having at least one of primary amino group, secondary amino group, or tertiary amino group in the molecule. You may have 2 or more types simultaneously.
• Examples of compounds having a primary amino group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, Aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like.
• Examples of compounds having a secondary amino group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, phenylethylamine and the like.
• Compounds having a tertiary amino group include, for example, triethylamine, tributylamine, trihexylamine, triallylamine, 3-diethylaminopropylamine, dibutylaminopropylamine, tetramethylethylenediamine, tri-n-octylamine, dimethylaminopropyl Amine, N,N-dimethylethanolamine, triethanolamine, N,N-diethylethanolamine, N-methyl-N,N-diethanolamine, N,N-dibutylethanolamine, triphenylamine, 4-methyltriphenylamine , 4,4-dimethyltriphenylamine, diphenylethylamine, diphenylbenzylamine, N,N-diphenyl-p-anisidine, 1,1,3,3-tetramethylguanidine, N,N-dicyclohexylmethylamine, 1,4 -diazabicyclo[2,2,2]oct
• the compound having two or more different amino groups in the same molecule at the same time is not particularly limited, but examples thereof include guanidine compounds and imidazole compounds.
• guanidine compounds include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine, 1,1,3,3-tetramethylguanidine and the like. be done.
• imidazole compounds include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4 -methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2, 4-diamino-6-(2′-methylimidazolyl-(1)′)-ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl
• the amine compound preferably contains a secondary or tertiary amino group.
• the amine compound more preferably contains a tertiary amino group.
• the amine compound is more preferably a tertiary amine compound.
• the amine compound preferably does not contain alkali metal, alkaline earth metal, transition metal elements and halogen elements.
• the amine compound preferably does not contain groups having active hydrogen such as hydroxy groups and sulfhydryl groups.
• the basic compound is solid at the time of curing, the reaction proceeds on the surface of the basic compound, and the reaction does not spread throughout the composition. become uneven. For this reason, it is preferred that the basic compound is not in a solid state at the time of curing, that is, in a liquid state or soluble in the resin composition.
• the molecular weight of the amine compound is preferably 100-1000, more preferably 100-500, still more preferably 110-300.
• the molecular weight of the amine compound is less than 100, the volatility is high, and there are concerns about the influence on peripheral members and the variation in physical properties of the cured product. If the molecular weight of the amine compound exceeds 1,000, there are concerns about an increase in the viscosity of the amine compound and a decrease in dispersibility in the composition.
• the basic compounds may be used alone or in combination of two or more.
• preferred amine compounds include triethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,1,3,3-tetramethylguanidine, N,N-dimethylbenzylamine, N-ethyl -N-methylbenzylamine, 2,6,10-trimethyl-2,6,10-triazaundecane, N,N-dimethyloctylamine, N,N-dimethyloctadecylamine and N,N-dimethyldodecylamine, N , N-diisopropylethylamine, N,N-dicyclohexylmethylamine, but are not limited thereto.
• the basic compound may be inactive by separation or latentiation, and may be activated by any stimulation such as heat, light, mechanical shear, and the like. More specifically, the basic compound may be a latent basic compound such as a microcapsule, an ion dissociation type, an inclusion type, etc., and is exposed to a base by heat, light, electromagnetic waves, ultrasound, or physical shear. may be in the form of generating
• the basic compound is a photobase generator.
• a photobase generator is a compound capable of generating a basic compound by a chemical reaction directly or indirectly involving light energy.
• the photobase generator may be used alone or in combination of two or more.
• the photobase generator is not particularly limited, but the photobase generator is excited by absorption of ultraviolet rays (preferably ultraviolet rays with a wavelength of 365 nm) to cause a chemical reaction to generate a basic compound, or It is preferable that the energy transferred from the photosensitizer excited by the absorption of ultraviolet light causes a chemical reaction to generate a basic compound.
• the photobase generator preferably has a structure that does not generate outgassing in principle.
• the photobase generator may be ionic or nonionic.
• the basic compound is heat activated.
• the basic compound is (i) physically separated from (A) the 2-methylene-1,3-dicarbonyl compound before heating and (A) 2-methylene-1 ,3-dicarbonyl compound, or (ii) is latent and non-basic (and thus does not act as a curing agent or curing catalyst) before heating, and Then it becomes basic.
• a basic compound is not particularly limited, it is preferred that the basic compound be activated by heating at 40-100°C.
• the present invention also provides a curable resin composition, particularly a one-component curable resin composition, containing the resin composition of the present invention and a latent basic compound or photobase generator.
• the resin composition of the present invention is used as a main component, and this is combined with a curing agent or curing catalyst containing one or more basic compounds to form a two-component mixed type curable resin composition (adhesive) kit.
• a two-component mixed type curable resin composition adheresive kit.
• the present invention also provides a kit of a two-part mixed type curable resin composition, comprising (A) the above resin composition; and (B) a curing agent or curing catalyst containing a basic compound.
• the two-liquid mixed curable resin composition kit of the present invention can be cured by bringing the main agent and the curing agent into contact with each other.
• the amount of the basic compound used is preferably 0.01 mol% to 30 mol with respect to the total amount (100 mol%) of (A) 2-methylene-1,3-dicarbonyl compound in the resin composition. %, more preferably 0.01 mol % to 10 mol %. If the amount of basic compound is less than 0.01 mol %, curing becomes unstable. Conversely, if the amount of the basic compound is more than 30 mol %, a large amount of the basic compound that does not form chemical bonds with the resin matrix will remain in the cured product, causing deterioration in physical properties of the cured product, bleeding, and the like.
• the resin composition of the present invention is cured by the action of a nucleophile such as an amine compound.
• a nucleophile such as an amine compound.
• Water can also act as a nucleophile in some cases, but the nucleophilicity (reactivity with electrophiles) of water is not as high as that of amine compounds. Therefore, the resin composition of the present invention usually does not harden even when in contact with water, and can be stored in a state in which it is in contact with air containing water vapor.
• Such properties of the resin composition of the present invention are such that (A) the electrophilicity (reactivity with nucleophiles) of the 2-methylene-1,3-dicarbonyl compound facilitates direct reaction with the amine compound.
• the resin composition of the present invention is mixed with (A) a substance that enhances the electrophilicity of the 2-methylene-1,3-dicarbonyl compound, the resin composition of the present invention is exposed to the atmosphere containing water vapor. May not be stored in contact.
• examples of such substances include Lewis acidic compounds.
• the Lewis acidic compound coordinates to the carbonyl oxygen of (A) 2-methylene-1,3-dicarbonyl compound and withdraws electrons, thereby obtaining (A) 2-methylene-1,3-dicarbonyl compound. It has the effect of enhancing electronicity.
• the resin composition of the present invention preferably does not contain Lewis acidic compounds, particularly Lewis acidic compounds containing monovalent to tetravalent metal cations.
• the resin composition of the present invention is substantially free of Lewis acidic compounds capable of coordinating to the carbonyl oxygen of (A) the 2-methylene-1,3-dicarbonyl compound.
• the resin composition of the present invention is substantially inert to atmospheric water and can be stored in contact with an atmosphere containing water vapor.
• the pot life of the curable resin composition can be evaluated, for example, by gelation time.
• gelation is a phenomenon in which the resin composition loses fluidity as the resin component increases in molecular weight through a chemical reaction.
• the gelling time is the time from when the curable resin composition becomes ready to start curing to when the curable resin composition loses fluidity under predetermined conditions.
• curing and curing time refer to the phenomenon of solidification to the extent that it is possible to hold and adhere objects more firmly and strongly as polymerization progresses, regardless of whether or not a crosslinked structure is formed. It is that time that has a different definition than gelling and gelling time.
• the resin composition of the present invention has a working life (gelation time) suitable for work.
• the gelation time (GT) of the resin composition means that 0.01 to 0.1 parts by mass of N,N-dimethylbenzylamine is added to 1 part by mass of the resin composition at 25 ° C. It is the time from mixing until the resin composition loses fluidity.
• Gelation time (GT) of the resin composition of the present invention is preferably 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes, particularly preferably 3 minutes to 15 minutes, still more preferably 4 to 10 minutes.
• the gelation time of the 2-methylene-1,3-dicarbonyl compound can be measured in the same manner as the gelation time (GT) of the resin composition. That is, in this specification, the gelation time (GT A ) of (A) 2-methylene-1,3-dicarbonyl compound is defined as (A) 2-methylene- After mixing 0.01 to 0.1 parts by mass of N,N-dimethylbenzylamine with 1 part by mass of the 1,3-dicarbonyl compound, (A) 2-methylene-1,3-dicarbonyl compound is the time until it loses liquidity.
• the GT A of (A) a 2-methylene-1,3-dicarbonyl compound is measured under the same conditions as the present invention containing the (A) 2-methylene-1,3-dicarbonyl compound.
• GT is longer than GT A when compared with the GT of the resin composition of the invention. That is, the resin composition of the present invention exhibits a prolonged gelation time (GT) compared to the gelation time (GT A ) of the (A) 2-methylene-1,3-dicarbonyl compound contained therein. show.
• the gelation time of the resin composition with respect to the gelation time (GT A ) of the (A) 2-methylene-1,3-dicarbonyl compound (GT) ratio (here, the ratio of the mass of N,N-dimethylbenzylamine to the mass of the resin composition in the measurement of GT is the ratio of (A) 2-methylene-1 in the measurement of GT A , equal to the mass ratio of N,N-dimethylbenzylamine to the mass of the 3-dicarbonyl compound) is preferably 1.1 to 3, more preferably 1.5 to 2.5, and particularly preferably is between 1.7 and 2.1.
• the resin composition of the present invention and the curable resin composition and kit using the resin composition of the present invention can be used as adhesives or sealing materials.
• it can be used as a one-component resin composition, a one-component adhesive or a sealing material.
• it can be used as a non-solvent type one-component resin composition, a non-solvent type one-component adhesive or sealing material.
• the resin composition, the curable resin composition and the kit are suitable as an adhesive or a sealing material for manufacturing electronic parts.
• the resin composition, curable resin composition and kit can be used for bonding and sealing camera module parts, and are particularly suitable for bonding sensor modules such as image sensor modules. .
• the present invention also provides an electronic component adhered using the above resin composition or a curable resin composition or kit using the resin composition. Furthermore, an electronic component encapsulated with the above resin composition, curable resin composition or kit is also provided. Moreover, the resin composition and the curable resin composition can be used both as an insulating composition and as a conductive composition.
• the present invention also provides a cured product obtained by curing the resin composition of the present invention or a curable resin composition or kit using the resin composition of the present invention as described above. An electronic component containing this cured product is also provided.
• a jet dispenser, an air dispenser, or the like can be used to supply the curable resin composition to the surface to be adhered.
• the curable resin composition can be cured at room temperature without heating.
• the curable resin composition can be cured by heating at a temperature of 25 to 80° C., for example.
• the heating temperature is preferably 50-80°C.
• the heating time is, for example, 0.01 to 4 hours.
• A-1 dihexyl methylene malonate (DHMM) (manufactured by SIRRUS, Chemilian (registered trademark) L3000 XP)
• A-2) Dicyclohexylmethylenemalonate (DCHMM) (manufactured by SIRRUS, Chemilian (registered trademark) H4000 XP)
• DCHMM Dicyclohexylmethylenemalonate
• (B) Fumed silica In the examples and comparative examples, the compounds used as (B) fumed silica are as follows.
• (C) Basic compound N,N-dimethylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 135.21)
• Examples 1 to 12 Comparative Examples 1 to 3
• A 2-methylene-1,3-dicarbonyl compound and (B) fumed silica (or (B') fumed silica other than (B) above) were mixed using a hybrid mixer. The latter was dispersed in the former to prepare a resin composition.
• Comparative Examples 1 and 2 are single compounds (unless unintentionally mixed impurities are considered), but are referred to as "resin compositions" here for convenience.
• the properties of the resin composition were measured as follows.
• the resin compositions of Examples 1 to 12 and Comparative Examples 1 to 3 with respect to the gelation time (GT A ) of component (A) (that is, the gelation time of the resin composition of Comparative Example 1 or Comparative Example 2) of the gelation time (GT) ratio (here, in the measurement of the GT, the ratio of the mass of N,N-dimethylbenzylamine to the mass of the resin composition is the ratio of the mass of the component (A) in the measurement of the GT A (equal to the ratio of the mass of N,N-dimethylbenzylamine to the mass of ) was calculated.
• Table 2 shows the results.
• the phrase "substantially loses fluidity" means that the content in the screw vial becomes so viscous that it cannot be stirred with a polypropylene stick.
• the resin composition of the present invention comprising (B) fumed silica having an average primary particle size and specific surface area within a predetermined range in combination with (A) a 2-methylene-1,3-dicarbonyl compound is suitable for operation.
• the gelation time (GT) of the resin composition of the present invention was evaluated as A) The gelling time (GT A ) of the 2-methylene-1,3-dicarbonyl compound (Comparative Examples 1 and 2) could be extended appropriately.
• the resin composition containing the 2-methylene-1,3-dicarbonyl compound of the present invention has a pot life (gelation time) and viscosity suitable for work, and is therefore useful for the production of various electronic components. In particular, it is useful for manufacturing electronic components that require high positional accuracy.

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• 2023
  • 2023-02-01 KR KR1020247022804A patent/KR20240141242A/ko active Pending
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