WO2024210093A1 - 硬化性組成物、硬化物、及び積層体 - Google Patents

硬化性組成物、硬化物、及び積層体 Download PDF

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WO2024210093A1
WO2024210093A1 PCT/JP2024/013458 JP2024013458W WO2024210093A1 WO 2024210093 A1 WO2024210093 A1 WO 2024210093A1 JP 2024013458 W JP2024013458 W JP 2024013458W WO 2024210093 A1 WO2024210093 A1 WO 2024210093A1
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group
curable composition
polymer
mass
reactive silicon
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French (fr)
Japanese (ja)
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旭卉 リュウ
佳孝 砂山
高 伊藤
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AGC Inc
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Asahi Glass Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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

Definitions

  • the present invention relates to a curable composition, a cured product, and a laminate.
  • This application claims priority based on Japanese Patent Application No. 2023-061834 filed in Japan on April 6, 2023, and Japanese Patent Application No. 2023-207556 filed in Japan on December 8, 2023, the contents of which are incorporated herein by reference.
  • Curable compositions containing 2-cyanoacrylate esters have a unique anionic polymerization property of the main component, 2-cyanoacrylate esters, which initiate polymerization with weak anions such as traces of moisture adhering to the surface of the adherend, allowing them to firmly bond various materials in a short time. For this reason, they are used as so-called instant adhesives in a wide range of fields, including industrial, medical, and household applications.
  • the cured product of this curable composition is hard and brittle, while it has excellent shear adhesive strength, it has low peel adhesive strength and impact adhesive strength, and is particularly poor in resistance to cold and heat cycles between different types of adherends.
  • bonding flexible adherends there is also the problem that the elongation of the adherends is lost.
  • Patent Document 1 describes an adhesive composition containing specific amounts of 2-cyanoacrylic acid ester, a polymer having a reactive silicon group, an elastomer, and an acid catalyst, and shows that the cured product has good elongation and strength before and after a thermal cycle test.
  • the comparative example in Patent Document 1 shows that 2-cyanoacrylic acid ester and a polymer having a reactive silicon group have poor compatibility, and gelation occurs when an elastomer is not used.
  • An object of the present invention is to provide a curable composition which does not gel during the mixing process of the curable composition and which gives a cured product which has good initial shear strength and good shear strength after a thermal cycle test.
  • a curable composition comprising a 2-cyanoacrylic acid ester and an oxyalkylene polymer having a reactive silicon group,
  • the oxyalkylene polymer has two or more end groups in one molecule, and the two or more end groups may be different from each other.
  • the terminal group contains a reactive silicon group represented by the following formula (1):
  • the terminal group having a reactive silicon group includes a divalent organic group containing a group represented by the following formula (i): Curable compositions.
  • R each independently represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group
  • X each independently represents a hydroxyl group, a halogen atom, or a hydrolyzable group.
  • a is an integer from 0 to 2.
  • R When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other.]
  • the oxyalkylene polymer preferably has an average of 0.6 to 50.0 reactive silicon groups per molecule, more preferably 1.0 to 10.0 reactive silicon groups, even more preferably 1.2 to 4.0 reactive silicon groups, and particularly preferably 1.5 to 3.0 reactive silicon groups.
  • the oxyalkylene polymer preferably has an average of 0.6 to 50.0 groups represented by formula (i) per molecule, more preferably 1.0 to 10.0 groups, and even more preferably 1.2 to 4.0 groups.
  • the oxyalkylene polymer is obtained by reacting a precursor polymer having at least two hydroxyl groups with a silylating agent having a reactive silicon group,
  • the curable composition according to any one of [1] to [5], wherein the oxyalkylene polymer has a structure represented by the following formula (A): R 10 -[L 10 -(Q 10 ) m -Si 10 ] n ...Formula (A)
  • R 10 is an organic group derived from the precursor polymer
  • L 10 is —O—C( ⁇ O)NH—
  • Q 10 is an alkylene group having 1 to 5 carbon atoms
  • Si 10 is a reactive silicon group represented by formula (1)
  • m is a number from 0 to 6
  • n is a number of 2 or more
  • in formula (A), n is preferably 2 or more and 50 or less
  • Si 10 in formula (1), R is an alkyl group having 1 to 4 carbon atoms,
  • X is an alk
  • the ratio of the 2-cyanoacrylic acid ester to the total mass of the curable composition is preferably 40 to 90 mass%, more preferably 45 to 85 mass%, and still more preferably 50 to 80 mass%.
  • the ratio of the oxyalkylene polymer to the total mass of the curable composition is preferably 1 to 50 mass%, more preferably 2 to 45 mass%, and even more preferably 4 to 40 mass%.
  • the proportion of the oxyalkylene polymer is preferably 5 to 200 parts by mass, more preferably 30 to 100 parts by mass, and even more preferably 45 to 55 parts by mass, relative to 100 parts by mass of the 2-cyanoacrylic acid ester.
  • the curable composition according to any one of [1] to [8].
  • the polymer is obtained by reacting a precursor polymer having at least two hydroxyl groups with a silylating agent having a reactive silicon group
  • the precursor polymer is preferably a polymer obtained by ring-opening addition polymerization of a cyclic ether compound having an epoxy group and a compound having at least two hydroxyl groups; more preferably a polymer obtained by ring-opening addition polymerization of ethylene oxide or propylene oxide and a dihydric polyhydric alcohol, a trihydric polyhydric alcohol, a tetrahydric polyhydric alcohol, a pentahydric polyhydric alcohol, a hexahydric polyhydric alcohol, a heptahydric or higher polyhydric alcohol, or a polyglycerin having 50 or less functional groups; more preferably a polymer obtained by ring-opening addition polymerization of ethylene oxide or propylene oxide and ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tri
  • the curable composition of the present invention does not gel during the mixing process, and the cured product has good initial shear strength and good shear strength after thermal cycle testing.
  • FIG. 2 is a cross-sectional view showing an example of a laminate.
  • the numerical range expressed by "-" means that the numerical values before and after "-" are the lower and upper limits of the numerical range.
  • the term "unsaturated group” refers to a monovalent group containing an unsaturated double bond. Unless otherwise specified, the unsaturated group is at least one group selected from the group consisting of a vinyl group, an allyl group, and an isopropenyl group.
  • the term "reactive silicon group” refers to a group represented by formula (1), which undergoes a dehydration condensation reaction with another reactive silicon group to form a siloxane bond (Si-O-Si), thereby forming a crosslinked structure within or between molecules of polymer A.
  • hydrolyzable group means a group that is converted into a hydroxy group by hydrolysis in the presence of water and an acid catalyst.
  • Oxyalkylene polymer means a polymer having a polyoxyalkylene chain formed from cyclic ether-based units. In an oxyalkylene polymer having a main chain containing a polyoxyalkylene chain and a terminal group bonded to the main chain, the term “terminal group” refers to an atomic group containing the oxygen atom that is closest to the molecular terminal of the oxyalkylene polymer among the oxygen atoms in the polyoxyalkylene chain.
  • the "active hydrogen-containing group” refers to at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a sulfanyl group, and a monovalent functional group formed by removing one hydrogen atom from a primary amine, which is bonded to a carbon atom.
  • active hydrogen refers to a hydrogen atom derived from the active hydrogen-containing group and a hydrogen atom derived from a hydroxyl group of water.
  • An “initiator” is a compound having two or more of the above active hydrogens.
  • the number average molecular weight (hereinafter, referred to as "Mn”) and weight average molecular weight (hereinafter, referred to as "Mw”) of the polymer are polystyrene equivalent molecular weights obtained by GPC measurement.
  • the molecular weight distribution is a value calculated from Mw and Mn, and is the ratio of Mw to Mn (hereinafter, referred to as "Mw/Mn").
  • the "hydroxyl value-based molecular weight" of a polymer is a value calculated by calculating the hydroxyl value of an initiator or a precursor polymer based on JIS K 1557 (2007) as "56,100/(hydroxyl value) ⁇ (number of active hydrogen atoms of an initiator, or number of terminal groups of a precursor polymer)".
  • the “silylation rate” is the ratio of the number of the reactive silicon groups to the total number of the terminal groups of the oxyalkylene polymer.
  • the lower limit and upper limit values described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the “preferable lower limit (10)” and the “more preferable upper limit (60)” to form “10 to 60.”
  • the curable composition of the present embodiment is a curable composition containing a 2-cyanoacrylic acid ester and an oxyalkylene polymer having a reactive silicon group.
  • the oxyalkylene polymer has two or more terminal groups in one molecule.
  • the terminal groups are groups having any of a reactive silicon group represented by the following formula (1), an unsaturated group, or a hydroxyl group, at least one of the terminal groups has the reactive silicon group, and the terminal group having the reactive silicon group contains a divalent organic group containing a group represented by the following formula (i).
  • R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group
  • X represents a hydroxyl group, a halogen atom, or a hydrolyzable group.
  • a is an integer from 0 to 2. When a is 2, R may be the same or different from one another, and when a is 0 or 1, X may be the same or different from one another.
  • any 2-cyanoacrylic acid ester generally used in a curable composition can be used without any particular limitation.
  • the total number of carbon atoms in the 2-cyanoacrylic acid ester is preferably 5 to 20, more preferably 5 to 16, and even more preferably 6 to 10.
  • R 1 is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, more preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and even more preferably a linear or branched alkyl group having 2 to 6 carbon atoms.
  • R 1 may be a methyl group, an ethyl group, a chloroethyl group, an n-propyl group, an i-propyl group, an allyl group, a propargyl group, an n-butyl group, an i-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a tetrahydrofurfuryl group, a heptyl group, a 2-ethylhexyl group, an n-octyl group, a 2-octyl group, an n-nonyl group, an oxonyl group, an n-decyl group, an n-dodecyl group, a methoxyethyl group, a methoxypropyl group, a methoxyisopropyl group, a methoxye
  • the polymer A is an oxyalkylene polymer having a polyoxyalkylene chain, two or more terminal groups in one molecule, and a reactive silicon group represented by the formula (1).
  • the terminal group has the reactive silicon group, an unsaturated group, or a hydroxyl group, and at least one of the terminal groups has the reactive silicon group.
  • the terminal group having the reactive silicon group contains a divalent organic group containing a group represented by the following formula (i).
  • the reactive silicon group is preferably bonded to the polyoxyalkylene chain via a divalent organic group (hereinafter also referred to as "organic group A") containing one group represented by the formula (i).
  • the curable composition may contain two or more types of polymer A.
  • the reactive silicon group has a hydroxyl group, a halogen atom, or a hydrolyzable group bonded to a silicon atom, and can form a siloxane bond to crosslink.
  • the reaction to form the siloxane bond is accelerated by a curing catalyst.
  • the reactive silicon group in polymer A is represented by the following formula (1). -SiR a X 3-a formula (1)
  • R represents a monovalent organic group having 1 to 20 carbon atoms.
  • R does not contain a hydrolyzable group.
  • R is preferably at least one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group, and a triorganosiloxy group.
  • R is preferably at least one selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an ⁇ -chloroalkyl group, and a triorganosiloxy group. It is more preferably at least one selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, an ⁇ -chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, and a triphenylsiloxy group.
  • a methyl group or an ethyl group is preferred because of the good curability of the polymer having a reactive silicon group and the stability of the curable composition.
  • An ⁇ -chloromethyl group is preferred because of the fast curing rate of the cured product.
  • a methyl group is particularly preferred because it is easily available.
  • X represents a hydroxyl group, a halogen atom, or a hydrolyzable group.
  • the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group.
  • the number of carbon atoms in the hydrolyzable group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3.
  • An alkoxy group is preferred because it is mildly hydrolyzable and easy to handle.
  • the alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group.
  • the alkoxy group is a methoxy group or an ethoxy group, it is easy to form a siloxane bond quickly and form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.
  • a is an integer of 0 to 2.
  • the Rs may be the same or different.
  • the Xs may be the same or different. It is preferable that a is 0 or 1, as this provides good curability.
  • Examples of the reactive silicon group represented by formula (1) include a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, and a methyldiethoxysilyl group.
  • the methyldimethoxysilyl group or the trimethoxysilyl group is preferred because of its high activity and good curability.
  • polymer A has a reactive silicon group represented by formula (1) above, a curable composition containing polymer A and an acid catalyst can be rapidly cured by moisture in the air, etc.
  • the main chain of polymer A has a polyoxyalkylene chain formed by polymerization of one or more types of cyclic ethers.
  • cyclic ethers include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide; and cyclic ethers other than alkylene oxides such as tetrahydrofuran. Among these, ethylene oxide and propylene oxide are preferred, and propylene oxide is more preferred.
  • the polyoxyalkylene chain may be a copolymer chain having two or more kinds of oxyalkylene groups.
  • the copolymer chain may be a block copolymer chain or a random copolymer chain.
  • Examples of the polyoxyalkylene chain of the polymer A include a polyoxypropylene chain, a polyoxyethylene chain, a poly(oxy-2-ethylethylene) chain, a poly(oxy-1,2-dimethylethylene) chain, a poly(oxytetramethylene) chain, a poly(oxyethylene-oxypropylene) chain, and a poly(oxypropylene-oxy-2-ethylethylene) chain.
  • a polyoxypropylene chain and a poly(oxyethylene-oxypropylene) chain are preferred, and a polyoxypropylene chain is more preferred.
  • poly(oxyethylene-oxypropylene) chain means a copolymer chain having two or more kinds of oxyalkylene groups, such as a copolymer chain having an oxyethylene group and an oxypropylene group.
  • the polymer A preferably has a structure represented by the following formula (A).
  • R 10 is an organic group derived from a precursor polymer; L 10 is —O—C( ⁇ O)NH—; Q 10 is an alkylene group having 1 to 5 carbon atoms; Si 10 is a reactive silicon group represented by formula (1); m is a number from 0 to 6; and n is a number of 2 or more.
  • n is preferably 2 to 50, more preferably 2 to 30, even more preferably 2 to 10, particularly preferably 2 to 6, and most preferably 2 to 3.
  • the polymer A has two or more end groups. From the viewpoint of improving the initial shear strength and elongation in a thermal cycle test of a cured product of the curable composition, the number of end groups of the polymer A is preferably 2 to 50, more preferably 2 to 10, still more preferably 2 to 4, and particularly preferably 2 or 3.
  • the terminal group of the polymer A has a reactive silicon group, an unsaturated group, or a hydroxyl group represented by the above formula (1). Each of the terminal groups may be the same or different.
  • the total number of reactive silicon groups, unsaturated groups and hydroxyl groups present in polymer A is preferably 1.0 to 1.4, more preferably 1.0 to 1.3, and even more preferably 1.0 to 1.2, on average per terminal group.
  • polymer A has an average of 0.3 or more reactive silicon groups per terminal group, preferably 0.3 to 2.0 reactive silicon groups, more preferably 0.3 to 1.3 reactive silicon groups, and even more preferably 0.4 to 1.0 reactive silicon groups per terminal group.
  • the number of the reactive silicon groups present in polymer A is preferably 0.6 to 50.0 on average per molecule, more preferably 1.0 to 10.0, even more preferably 1.2 to 4.0, and particularly preferably 1.5 to 3.0.
  • At least one end group of the polymer A has a reactive silicon group represented by the formula (1), and the end group having the reactive silicon group contains a divalent organic group containing a group represented by the following formula (i) (hereinafter also referred to as "group (i)").
  • the polymer A is preferably an oxyalkylene polymer having a reactive silicon group represented by the formula (1) bonded to a polyoxyalkylene chain via an organic group A containing one group (i).
  • the organic group A is an organic group derived from the below-described compound 1 used to introduce the reactive silicon group into an oxyalkylene polymer (precursor polymer) not having a reactive silicon group.
  • the group (i) is a divalent group derived from an isocyanate group contained in the compound 1.
  • group (i) polymer A is less likely to gel during the mixing step of the curable composition.
  • the number of reactive silicon groups per molecule of polymer A will be the same as the number of groups (i) per molecule.
  • the number of the groups (i) present in the polymer A is preferably from 0.6 to 50.0, more preferably from 1.0 to 10.0, and even more preferably from 1.2 to 4.0, on average per molecule.
  • a divalent organic group Q1 is present between the group (i) and the reactive silicon group.
  • Q1 is preferably a divalent hydrocarbon group, more preferably an alkylene group having 1 to 20 carbon atoms. A preferred embodiment of the organic group Q1 will be described later in relation to formula (2).
  • the Mn of polymer A is preferably 2,000 to 300,000, more preferably 5,000 to 100,000, even more preferably 10,000 to 50,000, and particularly preferably 10,000 to 30,000. If it is within this range, the elongation properties and initial shear strength of the cured product, as well as the shear strength in a thermal cycle test, tend to be good.
  • the molecular weight distribution of polymer A is preferably 1.80 or less. Since good elongation properties are easily obtained, a smaller molecular weight distribution is preferable, more preferably 1.00 to 1.50, even more preferably 1.00 to 1.40, and particularly preferably 1.05 to 1.20.
  • the silylation rate of polymer A is preferably 25 to 100 mol%, more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, and particularly preferably 80 to 100 mol%.
  • the average silylation rate of the entire polymer A is within the above range.
  • Polymer A can be obtained by introducing the reactive silicon group to the active hydrogen of the terminal group of a precursor polymer.
  • the precursor polymer is an oxyalkylene polymer obtained by ring-opening addition polymerization of a cyclic ether to the active hydrogen of an initiator having an active hydrogen-containing group in the presence of a ring-opening polymerization catalyst.
  • the number of active hydrogens in the initiator, the number of terminal groups in the precursor polymer, and the number of terminal groups in the polymer A are the same.
  • the precursor polymer is preferably a polymer having a hydroxyl group at the end, which is obtained by ring-opening addition polymerization of a cyclic ether to an initiator having a hydroxyl group.
  • the hydroxyl value-based molecular weight of the precursor polymer is preferably from 2,000 to 300,000, more preferably from 5,000 to 200,000, even more preferably from 10,000 to 100,000, and particularly preferably from 10,000 to 70,000. Within this range, the elongation properties and initial shear strength of the cured product, as well as shear strength in a thermal cycle test, tend to be good. Since polymer A is obtained by introducing the reactive silicon group to the active hydrogen of the terminal group of the precursor polymer, the hydroxyl value-based molecular weights of polymer A and the precursor polymer are almost the same.
  • the number of active hydrogen-containing groups in the initiator is preferably 2 or more.
  • the upper limit is preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less.
  • the active hydrogen-containing group in the initiator is preferably a hydroxyl group.
  • initiators having 2 to 50 active hydrogen-containing groups include dihydric polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and polyoxypropylene glycol having a molecular weight of 200 to 3,000; trihydric polyhydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, and polyoxypropylenetriol having a molecular weight of 200 to 3,000; 1,2,3,4-butanetetraol, pentaerythritol, diglycerin, sorbitan, ribose, arabinose, xylose, and lyxol.
  • dihydric polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tri
  • suitable polyhydric alcohols include tetrahydric alcohols such as glycerin, arabitol, xylitol, glucose, fructose, galactose, mannose, allose, gulose, idose, talose, and quercitol; pentahydric polyhydric alcohols such as dipentaerythritol, sorbitol, galactitol, mannitol, allitol, iditol, talitol, and inositol; heptahydric or higher polyhydric alcohols such as disaccharides (sucrose, etc.), polysaccharides (amylose, cellulose, starch, agar, pectin, xanthan gum, carrageenan, etc.), and hydrophobized polysaccharides (methylcellulose, methyl esterified pectin, etc.); and polyglycerin having 50 or less active hydrogen-containing groups.
  • the ring-opening polymerization catalyst when the cyclic ether is subjected to ring-opening addition polymerization to the initiator, a conventionally known catalyst can be used.
  • the ring-opening polymerization catalyst include an alkali catalyst such as KOH, a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound with porphyrin, a composite metal cyanide complex catalyst, and a catalyst composed of a phosphazene compound.
  • a composite metal cyanide complex catalyst is preferred because it can narrow the molecular weight distribution of the polymer A and is easy to obtain a curable composition with low viscosity.
  • a conventionally known compound can be used as the composite metal cyanide complex catalyst, and a known method can be adopted as a method for producing a polymer using a composite metal cyanide complex.
  • a known method can be adopted as a method for producing a polymer using a composite metal cyanide complex.
  • compounds and production methods disclosed in WO 2003/062301, WO 2004/067633, JP 2004-269776 A, JP 2005-15786 A, WO 2013/065802 A, and JP 2015-010162 A can be used.
  • the precursor polymer of the polymer A a precursor polymer in which all terminal groups are hydroxyl groups is preferred.
  • the method for producing the polymer A includes the following methods (a) and (b).
  • the compound 1 to be reacted with the precursor polymer in the above-mentioned method (a) is represented by the following formula (2).
  • Formula (2) In formula (2), R, X, and a are the same as R, X, and a in formula (1), including preferred embodiments thereof.
  • Q1 is a divalent organic group having 1 to 20 carbon atoms.
  • Q1 is preferably a divalent hydrocarbon group, more preferably an alkylene group.
  • Q1 preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms.
  • Examples of compound 1 include isocyanate methyl trimethoxysilane, isocyanate methyl triethoxysilane, isocyanate methyl methyl dimethoxysilane, 3-isocyanate propyl methyl dimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl methyl diethoxysilane, and 3-isocyanate propyl triethoxysilane.
  • the cured product of the curable composition has superior initial shear strength and shear strength in a thermal cycle test
  • 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, and 3-isocyanatepropyltriethoxysilane are preferred.
  • the active hydrogen of the precursor polymer reacts with the isocyanate group of compound 1, thereby introducing a reactive silicon group into the precursor polymer.
  • the active hydrogen-containing group of the precursor polymer is a hydroxyl group
  • the reaction of the precursor polymer with compound 1 in the above-mentioned method (a) can be carried out by a known method.
  • a known urethanization catalyst may be used in the reaction (urethanization reaction) of the precursor polymer with compound 1.
  • the urethanization catalyst may be an organic tin compound, a bismuth compound, a metal organic alkoxide, a complex containing a metal other than tin, an organic amine, or a composite metal cyanide complex catalyst having an organic ligand.
  • the urethanization catalyst is preferably dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin bisisooctylthioglycol, or bismuth octylate.
  • the molar ratio of the total number of isocyanate groups in compound 1 to the total number of active hydrogens in the precursor polymer is preferably set according to the number of reactive silicon groups per molecule of the polymer A to be obtained.
  • Compound 1 is reacted so that the number of reactive silicon groups per terminal group of the resulting polymer A is at least 0.5 on average.
  • NCO/OH which represents the molar ratio of the total number of isocyanate groups (NCO) of compound 1 to the total number of hydroxyl groups of the precursor polymer, is preferably 0.5 to 1.2, more preferably 0.6 to 1.1, and even more preferably 0.8 to 1.0.
  • the polyisocyanate compound is a diisocyanate compound represented by the following formula (3) and that the silylating agent having a functional group capable of reacting with an isocyanate group and a reactive silicon group represented by the above formula (1) is a compound represented by the following formula (4), but the present invention is not limited thereto.
  • R3 represents a divalent organic group.
  • W is a functional group capable of reacting with a monovalent isocyanate group (a group having one or more active hydrogens)
  • R 4 is a divalent organic group
  • -SiR a X 3-a is the above This is the same as equation (1).
  • the urethane bond and reactive silicon group-containing group have two urethane bonds.
  • R3 is preferably a divalent organic group having 2 to 20 carbon atoms, and examples thereof include an alkylene group, a cycloalkylene group, a bicycloalkylene group, a monocyclic or polycyclic divalent aromatic hydrocarbon group, a divalent group obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more cycloalkanes which may have an alkyl group as a substituent and are bonded via an alkylene group, and a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons which may have an alkyl group as a substituent and are bonded via an alkylene group.
  • diisocyanate compound represented by the above formula (3) and other polyisocyanate compounds examples include aromatic polyisocyanates, non-yellowing aromatic polyisocyanates (which refer to compounds that do not have an isocyanate group directly bonded to a carbon atom constituting an aromatic ring), aliphatic polyisocyanates and alicyclic polyisocyanates, as well as urethane-modified products, biuret-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products obtained from the above polyisocyanates.
  • aromatic polyisocyanates non-yellowing aromatic polyisocyanates (which refer to compounds that do not have an isocyanate group directly bonded to a carbon atom constituting an aromatic ring)
  • aliphatic polyisocyanates and alicyclic polyisocyanates as well as urethane-modified products, biuret-modified products, allophanate-modified products, carbodiimi
  • aromatic polyisocyanates examples include naphthalene-1,5-diisocyanate, polyphenylenepolymethylene polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
  • non-yellowing aromatic polyisocyanates include xylylene diisocyanate and tetramethylxylylene diisocyanate.
  • the aliphatic polyisocyanate examples include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate.
  • alicyclic polyisocyanates examples include isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate).
  • the polyisocyanate compound is preferably one having two isocyanate groups, and hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate are preferred, with tolylene diisocyanate being more preferred because it is easier to obtain a tensile strength of the cured product.
  • One type of polyisocyanate compound may be used, or two or more types may be used in combination.
  • R 4 in the silylating agent having a functional group capable of reacting with an isocyanate group represented by formula (4) and -SiX a R 3-a is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms and substituted with an alkyl group having 1 to 4 carbon atoms, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms, or a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 12 carbon atoms, still more preferably a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 8 carbon atoms, and particularly preferably a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 6 carbon atoms.
  • W is preferably a group having one or two active hydrogens selected from a hydroxyl group, a carboxyl group, a sulfanyl group, an amino group, and an amino group in which one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms, more preferably a hydroxyl group, a sulfanyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group, and more preferably a hydroxyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group.
  • the curable composition can be obtained by mixing the 2-cyanoacrylic ester, the polymer A, and other necessary components.
  • the curable composition is cured to form a cured product, a sea-island structure is formed between the polymer containing a structural unit derived from a 2-cyanoacrylate ester and polymer A.
  • polymer A is crosslinked via siloxane bonds (Si—O—Si bonds) within and between the molecules of polymer A.
  • the proportion of the 2-cyanoacrylic acid ester relative to the total mass of the curable composition is preferably 40 to 90 mass%, more preferably 45 to 85 mass%, and even more preferably 50 to 80 mass%.
  • the cured product of the curable composition has excellent curability and initial shear strength.
  • the proportion of polymer A relative to the total mass of the curable composition is preferably 1 to 50 mass%, more preferably 2 to 45 mass%, further preferably 4 to 40 mass%, and particularly preferably 10 to 35 mass%.
  • the cured product of the curable composition has excellent initial shear strength and shear strength after a thermal cycle test.
  • the total content of the 2-cyanoacrylic acid ester and polymer A relative to the total mass of the curable composition is preferably 50 to 100 mass%, more preferably 65 to 99 mass%, and even more preferably 80 to 99 mass%.
  • the cured product of the curable composition has excellent curability and initial shear strength.
  • the proportion of polymer A is preferably 5 to 200 parts by mass, more preferably 30 to 100 parts by mass, and even more preferably 45 to 55 parts by mass, relative to 100 parts by mass of the 2-cyanoacrylic acid ester. Within this range, the cured product of the curable composition has good curability.
  • Examples of other components besides the 2-cyanoacrylate ester and polymer A include those that have been conventionally blended into curable compositions containing a 2-cyanoacrylate ester.
  • elastomers, acid catalysts, silane coupling agents, anionic polymerization accelerators, radical polymerization inhibitors, plasticizers, thickeners, fumed silica, particles, fillers, colorants, fragrances, solvents, and strength improvers can be blended in appropriate amounts depending on the purpose, etc., within a range that does not impair the curability and adhesive strength, etc., of the curable composition.
  • the elastomer has rubber elasticity at about room temperature (20°C ⁇ 15°C) and is preferably solid.
  • the elastomer is not particularly limited as long as it is soluble in both the 2-cyanoacrylic acid ester and the polymer A.
  • the 2-cyanoacrylic acid ester and the polymer A can be stably compatible with each other due to the presence of the elastomer.
  • the elastomer examples include acrylic acid ester copolymers, acrylonitrile-styrene copolymers, acrylonitrile-butadiene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, ethylene-acrylic acid ester copolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polyurethane copolymers, polyester copolymers, fluorine copolymers, polyisoprene copolymers, and chloroprene copolymers. These may be used alone or in combination of two or more.
  • copolymers made using monomers that can become polymers that are poorly soluble in 2-cyanoacrylic acid esters, and monomers that can become polymers that are soluble in 2-cyanoacrylic acid esters (excluding the carboxyl group-containing monomers described below). These copolymers have poorly soluble segments formed by the polymerization of monomers that can become polymers that are poorly soluble in 2-cyanoacrylic acid esters, and soluble segments formed by the polymerization of monomers that can become polymers that are soluble in 2-cyanoacrylic acid esters.
  • Monomers that can become polymers that are poorly soluble in 2-cyanoacrylic acid esters are not particularly limited, and examples include ethylene, propylene, isoprene, butadiene, chloroprene, 1-hexene, and cyclopentene. These monomers may be used alone or in combination of two or more. Ethylene, propylene, isoprene, butadiene, and chloroprene are often used as monomers that can become polymers that are poorly soluble, and at least one of ethylene, propylene, isoprene, and butadiene is preferable.
  • the monomer that can become a polymer soluble in 2-cyanoacrylic acid ester is not particularly limited, and examples thereof include acrylic acid ester, methacrylic acid ester, vinyl chloride, vinyl acetate, vinyl ether, styrene, and acrylonitrile, and it is preferable to use at least one of acrylic acid ester and methacrylic acid ester.
  • acrylic acid ester examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxyethyl acrylate, and ethoxypropyl acrylate. These monomers may be used alone or in combination of two or more.
  • methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, ethoxyethyl methacrylate, and ethoxypropyl methacrylate. Only one of these monomers may be used, or two or more of them may be used in combination. Also, acrylic acid esters and methacrylic acid esters may be used in combination.
  • the ratio of the poorly soluble segment formed by polymerization of a monomer capable of forming a poorly soluble polymer and the soluble segment formed by polymerization of a monomer capable of forming a soluble polymer is not particularly limited, and when the total of these segments is taken as 100 mol%, the poorly soluble segment may be 5 to 90 mol%, preferably 10 to 80 mol%, and the soluble segment may be 10 to 95 mol%, preferably 20 to 90 mol%.
  • the ratio is preferably 30 to 80 mol% for the poorly soluble segment, 20 to 70 mol% for the soluble segment, particularly 40 to 80 mol% for the poorly soluble segment, 20 to 60 mol% for the soluble segment, and more preferably 50 to 75 mol% for the poorly soluble segment, and 25 to 50 mol% for the soluble segment.
  • the poorly soluble segment is 5 to 90 mol % and the soluble segment is 10 to 95 mol %, and particularly when the poorly soluble segment is 30 to 80 mol % and the soluble segment is 20 to 70 mol %, the copolymer can be appropriately dissolved in the 2-cyanoacrylate ester, and a curable composition having both high shear adhesive strength and excellent thermal cycle resistance can be obtained.
  • the proportion of each segment can be calculated from the integral value of protons measured by proton nuclear magnetic resonance spectroscopy (hereinafter referred to as "1H-NMR").
  • copolymers made of monomers capable of forming polymers poorly soluble in 2-cyanoacrylic acid esters, monomers capable of forming polymers soluble in 2-cyanoacrylic acid esters, and carboxyl group-containing monomers.
  • carboxyl group-containing monomers may be contained in this copolymer.
  • the carboxyl group-containing monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. These monomers may be used alone or in combination of two or more.
  • Acrylic acid and methacrylic acid are often used as carboxyl group-containing monomers, and either one of these may be used or they may be used in combination.
  • the carboxyl group-containing segment formed by polymerization of this carboxyl group-containing monomer becomes a segment soluble in highly hydrophilic 2-cyanoacrylic acid esters.
  • the proportion of the carboxyl group-containing segment is not particularly limited, but is preferably 0.1 to 5 mol%, particularly 0.3 to 4 mol%, and further preferably 0.4 to 3 mol%, when the total of the poorly soluble segment, the soluble segment, and the carboxyl group-containing segment is taken as 100 mol%. Moreover, this content is more preferably 0.5 to 2.5 mol%, particularly preferably 0.5 to 2.3 mol%.
  • the carboxyl group-containing segment is 0.1 to 5 mol%, particularly preferably 0.5 to 2.5 mol%, it is possible to obtain a curable composition that cures quickly after application to an adherend and has excellent resistance to cold and heat cycles and hot water resistance.
  • the proportion of the carboxy group-containing segment can be measured by potentiometric titration or indicator titration in accordance with JIS K0070 (1992).
  • examples of the copolymers that can be used include ethylene/methyl acrylate copolymers, ethylene/methyl acrylate/butyl acrylate copolymers, ethylene/methyl methacrylate copolymers, ethylene/vinyl acetate copolymers, butadiene/methyl acrylate copolymers, butadiene/acrylonitrile copolymers, butadiene/acrylonitrile/acrylic acid ester copolymers, and butadiene/styrene/acrylonitrile/methyl acrylate copolymers.
  • ethylene/methyl acrylate copolymers and ethylene/methyl acrylate/butyl acrylate copolymers are particularly preferred.
  • copolymers obtained by polymerizing the monomers used in each of the above copolymers with carboxyl group-containing monomers such as acrylic acid and/or methacrylic acid can be used. These copolymers may be used alone or in combination of two or more, and a copolymer without a carboxyl group-containing monomer and a copolymer with a carboxyl group-containing monomer may be used in combination.
  • Commercially available elastomers can be used. For example, the Vamac series manufactured by DuPont Corporation can be mentioned.
  • the number average molecular weight of the elastomer is not particularly limited, but it is preferable that the number average molecular weight (Mn) is 5,000 to 500,000, particularly 15,000 to 150,000, and further 20,000 to 100,000. If the number average molecular weight of the elastomer is within the above range, the elastomer dissolves easily in 2-cyanoacrylic acid ester, and a curable composition having high adhesive strength, particularly after a thermal cycle test, can be obtained.
  • the weight average molecular weight (Mw) of the elastomer is preferably 5,000 to 1,000,000, particularly 10,000 to 1,000,000, and Mw/Mn is preferably 1.00 to 10.0, particularly 1.00 to 8.0.
  • the curable composition does not contain an elastomer, or if it contains an elastomer, the content of the elastomer is 20 parts by mass or less per 100 parts by mass of the 2-cyanoacrylic acid ester.
  • the content of the elastomer is more preferably more than 0 parts by mass and 5 parts by mass or less, and even more preferably more than 0 parts by mass and 3 parts by mass or less, per 100 parts by mass of the 2-cyanoacrylic acid ester. It is particularly preferable that the curable composition does not contain an elastomer.
  • the content of the elastomer component is within the above range, the time for the 2-cyanoacrylic acid ester and the polymer A to become compatible can be significantly shortened, the production process can be shortened, and a curable composition having excellent adhesive function can be obtained.
  • the content of the elastomer per 100 parts by mass of polymer A is more preferably more than 0 parts by mass and not more than 10 parts by mass, and even more preferably more than 0 parts by mass and not more than 5 parts by mass. It is particularly preferable that no elastomer is contained.
  • the time required for the 2-cyanoacrylic acid ester and polymer A to become compatible can be significantly shortened, thereby realizing a shortening of the production process and providing a curable composition having excellent adhesive function.
  • the curable composition may contain an acid catalyst.
  • the acid catalyst is a curing catalyst for the polymer A.
  • the acid catalyst is preferably an acid having a pKa of 4 or less at 25° C.
  • the pKa is more preferably 3.0 or less. If the acid has a pKa of 4 or less, the curable composition will be cured at a speed suitable for practical use.
  • the acid catalyst include sulfonic acid, aliphatic sulfonic acids such as methanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, phosphoric acid, phosphoric acid monoesters, phosphoric acid diesters, phosphorous acid, and phosphorous acid esters.
  • sulfonic acid aliphatic sulfonic acids such as methanesulfonic acid, phosphoric acid, phosphoric acid monoesters, and phosphoric acid diesters are preferred.
  • aliphatic sulfonic acids such as methanesulfonic acid and aromatic sulfonic acids such as p-toluenesulfonic acid also function as polymerization inhibitors for 2-cyanoacrylic acid esters.
  • the content of the acid catalyst is preferably 0.001 to 1.0 part by mass, more preferably 0.002 to 0.8 parts by mass, and even more preferably 0.003 to 0.6 parts by mass, based on 100 parts by mass of Polymer A.
  • the content of the acid catalyst is within the above range, good curability is obtained, and the storage stability of the curable composition is excellent.
  • the content of the acid catalyst is preferably 0.05 to 100 mol, more preferably 0.1 to 85 mol, and even more preferably 0.2 to 65 mol, relative to 100 mol of the total number of reactive silicons contained in polymer A.
  • the curable composition may contain a silane coupling agent (also called a “storage stabilizer” or “dehydrating agent” depending on the purpose) for the purpose of improving adhesion and storage stability or obtaining a dehydrating effect for suppressing hydrolysis of the polymer A.
  • a silane coupling agent also called a “storage stabilizer” or “dehydrating agent” depending on the purpose
  • the silane coupling agent a wide variety of known silane coupling agents can be used.
  • acrylic silanes such as ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, ⁇ -acryloxypropylmethyldimethoxysilane, and ⁇ -acryloxypropylmethyldiethoxysilane
  • mercaptosilanes such as ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane
  • ⁇ -ureidopropyltriethoxysilane methyltrimethoxysilane, vinyltrimethoxysilane, and the like
  • silane coupling agents may be used alone or in combination of two or more kinds.
  • the amount of the silane coupling agent used is preferably 0.1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, relative to 100 parts by mass of Polymer A. If the amount of the silane coupling agent is within the above range, high adhesion, sufficient storage stability, and dehydration effect can be obtained, which is preferable.
  • the amount of the dehydrating agent used is preferably 0.1 to 20 parts by mass, and more preferably 3 to 7 parts by mass, relative to 100 parts by mass of Polymer A. If the amount of the silane coupling agent is within the above range, high adhesion, sufficient storage stability, and dehydrating effect can be obtained, which is preferable.
  • anionic Polymerization Accelerator examples include polyalkylene oxides, crown ethers, silacrown ethers, calixarenes, cyclodextrins, and pyrogallol-based cyclic compounds.
  • the polyalkylene oxides are polyalkylene oxides and derivatives thereof, such as those disclosed in JP-B-60-37836, JP-B-1-43790, JP-A-63-128088, JP-A-3-167279, U.S. Pat. No. 4,386,193, and U.S. Pat. No. 4,424,327.
  • polyalkylene oxides include (1) polyalkylene oxides such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol, and (2) derivatives of polyalkylene oxides such as polyethylene glycol monoalkyl esters, polyethylene glycol dialkyl esters, polypropylene glycol dialkyl esters, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.
  • examples of crown ethers include those disclosed in JP-B-55-2236 and JP-A-3-167279.
  • silacrown ethers examples include those disclosed in JP-A-60-168775 etc. Specific examples include dimethylsila-11-crown-4, dimethylsila-14-crown-5, dimethylsila-17-crown-6 etc.
  • calixarenes examples include those disclosed in JP-A-60-179482, JP-A-62-235379, JP-A-63-88152 etc.
  • cyclodextrins include those disclosed in Japanese Patent Publication No. 5-505835 and the like. Specific examples include ⁇ -, ⁇ -, and ⁇ -cyclodextrin.
  • pyrogallol-based cyclic compounds include the compounds disclosed in JP-A-2000-191600 and the like. Specific examples include 3,4,5,10,11,12,17,18,19,24,25,26-dodecaethoxycarbomethoxy-C-1,C-8,C-15,C-22-tetramethyl[14]-metacyclophane and the like. These anionic polymerization accelerators may be used alone or in combination of two or more.
  • polymerization inhibitor examples include (1) boron trifluoride complexes such as boron trifluoride methanol and boron trifluoride diethyl ether, HBF4 , and anionic polymerization inhibitors such as trialkyl borates, and (2) radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, catechol, and pyrogallol. These polymerization inhibitors may be used alone or in combination of two or more.
  • boron trifluoride complexes such as boron trifluoride methanol and boron trifluoride diethyl ether, HBF4
  • anionic polymerization inhibitors such as trialkyl borates
  • radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, catechol, and pyrogallol.
  • the content of the polymerization inhibitor is preferably 0.005 to 1.0 part by mass, more preferably 0.005 to 0.8 part by mass, and even more preferably 0.005 to 0.5 part by mass, relative to 100 parts by mass of the 2-cyanoacrylic acid ester.
  • the content of the polymerization inhibitor is within the above range, good curability is obtained, and the storage stability of the curable composition is excellent.
  • the plasticizer can be contained within a range that does not impair the effects of the present invention.
  • a copolymer containing a large amount of monomers that can become a poorly soluble polymer is used as the elastomer component, that is, a copolymer containing a large amount of poorly soluble segments (a copolymer in which the proportion of poorly soluble segments is 65 mol % or more)
  • the solubility can be improved by containing an appropriate amount of plasticizer.
  • plasticizer examples include triethyl acetyl citrate, tributyl acetyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, diisotridecyl phthalate, dipentadecyl phthalate, dioctyl terephthalate, diisononyl isophthalate, decyl toluate, bis(2-ethylhexyl) camphorate, 2-ethylhexyl cyclohexyl carboxylate, diisobutyl fumarate, diisobutyl maleate, triglyceride
  • plasticizers may be used alone or in combination of two or more.
  • the content of the plasticizer is not particularly limited, but is preferably 3 to 50 parts by mass, particularly 10 to 45 parts by mass, and further preferably 20 to 40 parts by mass, based on 100 parts by mass of 2-cyanoacrylic acid ester.
  • the copolymer can be easily dissolved in the 2-cyanoacrylic acid ester, particularly when the elastomer component is a copolymer having a large number of poorly soluble segments, and the retention rate of the adhesive strength in the thermal cycle resistance test can be improved.
  • thickener examples include polymethyl methacrylate, copolymers of methyl methacrylate and acrylic esters, copolymers of methyl methacrylate and other methacrylic esters, acrylic rubber, polyvinyl chloride, polystyrene, cellulose ester, polyalkyl-2-cyanoacrylate, and ethylene-vinyl acetate copolymers, etc. These thickeners may be used alone or in combination of two or more.
  • the curable composition may contain fumed silica.
  • the fumed silica is anhydrous silica in the form of ultrafine powder (primary particle diameter is 500 nm or less, particularly 1 to 200 nm).
  • the anhydrous silica is anhydrous silica in the form of ultrafine powder (primary particle diameter is 500 nm or less, particularly 1 to 200 nm) that is produced, for example, from silicon tetrachloride as a raw material by oxidation in a gas phase in a high-temperature flame, and includes hydrophilic silica with high hydrophilicity and hydrophobic silica with high hydrophobicity.
  • the fumed silica either type can be used, but hydrophobic silica is preferred because of its good dispersibility in 2-cyanoacrylic acid ester.
  • a copolymer containing a large amount of monomers that can become a polymer soluble in 2-cyanoacrylic acid ester is used as the elastomer component, that is, a copolymer containing a large amount of soluble segments (including carboxyl group-containing segments), it is preferable to use hydrophilic silica in combination.
  • hydrophobic silica when a copolymer containing a large amount of monomers that can become a poorly soluble polymer is used as the elastomer component, that is, a copolymer containing a large amount of poorly soluble segments, it is preferable to use hydrophobic silica in combination.
  • hydrophilic silica various commercially available products can be used, for example, Aerosil 50, 130, 200, 300 and 380 (these are trade names, manufactured by Nippon Aerosil Co., Ltd.).
  • the specific surface areas of these hydrophilic silicas are 50 ⁇ 15 m 2 /g, 130 ⁇ 25 m 2 /g, 200 ⁇ 25 m 2 /g, 300 ⁇ 30 m 2 /g, and 380 ⁇ 30 m 2 /g, respectively.
  • Reolosil QS-10, QS-20, QS-30 and QS-40 (these are trade names, manufactured by Tokuyama Corporation), etc. can be used.
  • hydrophilic silicas are 140 ⁇ 20 m 2 /g, 220 ⁇ 20 m 2 /g, 300 ⁇ 30 m 2 /g, and 380 ⁇ 30 m 2 /g, respectively.
  • hydrophilic silica such as that manufactured by CABOT Co., Ltd.
  • the specific surface area of the hydrophilic silica is preferably 20 to 600 m 2 /g.
  • hydrophobic silica a product can be used which is produced by contacting hydrophilic silica with a compound capable of reacting with hydroxyl groups present on the surface of the hydrophilic silica to form hydrophobic groups, or with a compound capable of being adsorbed on the surface of the hydrophilic silica to form a hydrophobic layer on the surface, in the presence or absence of a solvent, and preferably heating the mixture to treat the surface of the hydrophilic silica.
  • Compounds used to surface treat hydrophilic silica to make it hydrophobic include various alkyl, aryl, and aralkyl silane coupling agents having hydrophobic groups such as n-octyltrialkoxysilane, silylating agents such as methyltrichlorosilane, dimethyldichlorosilane, and hexamethyldisilazane, silicone oils such as polydimethylsiloxane, higher alcohols such as stearyl alcohol, and higher fatty acids such as stearic acid.
  • hydrophobic silica products that have been hydrophobized using any of these compounds may be used.
  • hydrophobic silica examples include Aerosil RY200 and R202 which have been surface-treated with silicone oil and hydrophobized, Aerosil R974, R972, and R976 which have been surface-treated with a dimethylsilylation agent and hydrophobized, Aerosil R805 which has been surface-treated with n-octyltrimethoxysilane and hydrophobized, Aerosil R811 and R812 which have been surface-treated with a trimethylsilylation agent and hydrophobized (all of these are trade names, manufactured by Nippon Aerosil Co., Ltd.), and Reolosil MT-10 which has been surface-treated with methyltrichlorosilane and hydrophobized (trade name, manufactured by Tokuyama Corporation).
  • the specific surface areas of these hydrophobic silicas are 100 ⁇ 20 m 2 /g, 100 ⁇ 20 m 2 /g, 170 ⁇ 20 m 2 /g, 110 ⁇ 20 m 2 /g, 250 ⁇ 25 m 2 /g, 150 ⁇ 20 m 2 /g, 150 ⁇ 20 m 2 /g, 260 ⁇ 20 m 2 /g, and 120 ⁇ 10 m 2 /g, respectively.
  • the specific surface area of the hydrophobic silica is preferably 20 to 400 m 2 /g.
  • the preferred content of fumed silica in the curable composition is 1 to 30 parts by mass, based on 100 parts by mass of 2-cyanoacrylic acid ester.
  • a more preferred content of this fumed silica is 1 to 25 parts by mass, and a particularly preferred content is 2 to 20 parts by mass, depending on the type of 2-cyanoacrylic acid ester, the type and ratio of monomers used in the production of the elastomer, and the type of fumed silica. If the content of fumed silica is within the above range, the curability and adhesive strength of the curable composition are not impaired, and the curable composition has good workability.
  • the cured product is a product of curing the curable composition.
  • the cured product can be produced by curing the curable composition with moisture in the air.
  • the cured product of the present embodiment has high initial shear strength and good shear strength and elongation in a thermal cycle test. Specifically, in a tensile shear test described later, a maximum stress (Tmax), which is an index of shear strength in the early stage of curing, of 1.4 [N/mm 2 ] or more can be achieved. In addition, in a thermal cycle test described later, it is possible to achieve Tmax of 1.3 [N/mm 2 ] or more and elongation at maximum stress (Emax) of 0.4 [mm] or more.
  • the maximum stress (Tmax) measured in a tensile shear test described later is preferably 1.4 [N/mm 2 ] or more, more preferably 2.0 [N/mm 2 ] or more, and even more preferably 2.5 [N/mm 2 ] or more.
  • the Tmax measured in a thermal cycle test described later is preferably 1.3 [N/mm 2 ] or more, more preferably 1.5 [N/mm 2 ] or more, and even more preferably 2.0 [N/mm 2 ] or more.
  • the elongation at maximum stress (Emax) measured in a thermal cycle test described later is preferably 0.4 mm or more, more preferably 0.6 mm or more, and even more preferably 1.0 mm or more.
  • the curable composition is suitable for use as an adhesive.
  • it can be used as a so-called instant adhesive in a wide range of products and technical fields, including general household and medical fields, as well as in various industrial sectors. It is particularly useful in applications that require adhesive durability, such as resistance to thermal cycles and high initial shear strength of the cured product.
  • the laminate comprises a cured product obtained by curing a curable composition and a substrate.
  • 1 is a cross-sectional view showing an example of the laminate of the present invention.
  • the laminate 1 of the present invention includes a cured product 2 obtained by curing the curable composition of the present invention, and a substrate 3.
  • the laminate is formed by contacting at least one substrate with the cured product over a part or the whole of the substrate surface.
  • the substrate include ABS (acrylonitrile-butadiene-styrene copolymer), aluminum, PVC, polycarbonate, polypropylene, polyethylene, polyacetal, acrylic, wood, and iron, and ABS or aluminum is preferred.
  • the substrate is preferably in the form of a plate.
  • the curable composition when the curable composition is dropped or applied onto a substrate, it reacts with moisture in the air and quickly cures to obtain a laminate in which the cured product (adhesive layer) and the substrate are bonded together.
  • the curable composition is sandwiched between two substrates and cured, a laminate in which the two substrates are integrated via the cured product (adhesive layer) is obtained.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) of the oxyalkylene polymer are polystyrene-equivalent molecular weights obtained by GPC measurement.
  • the molecular weight distribution (Mw/Mn) is a value calculated from Mw and Mn.
  • the silylation rate (mol %) was defined as the amount of reactive silicon group of the silylating agent charged relative to the unsaturated group introduced into the terminal group.
  • the amount of unsaturated groups that do not react with the silylating agent due to side reactions is approximately 10 mol %.
  • the silylation rate (mol %) was defined as the charge equivalent of the isocyanate groups of the isocyanate silane compound relative to the hydroxyl groups of the precursor polymer.
  • the curable composition contains an elastomer
  • the 2-cyanoacrylic acid ester premixed with the polymerization inhibitor and the elastomer were put into a bio bottle and stirred at room temperature with a magnetic stirrer. After the stirring started, the mixture was visually observed every hour. After the elastomer was completely dissolved and the mixture became a transparent liquid, the polymer mixture was added and further stirred.
  • the mixture was visually observed every 5 minutes. The state in which neither gel-like matter nor phase separation was observed was judged to be in a compatible state. In addition, when a gel-like matter was observed, it was judged to have gelled, and the presence or absence of gelling during the mixing process of the curable composition was recorded as " ⁇ " when it did not gel and " ⁇ " when it gelled. The time from the start of stirring after the elastomer was added until it was judged to be in a compatible state was recorded as the measurement result. In both cases, the stirring conditions were as follows: a Koike Precision Machinery Manufacturing Co., Ltd. product name "KPI Mighty Stirrer" was used, speed control was set to "5", and the rotation speed was set to about 700 rpm.
  • the prepared test piece was cured for 7 days in an atmosphere at a temperature of 23°C and a relative humidity of 50%, to obtain a laminate.
  • a tensile shear test was carried out for each laminate in accordance with JIS K 6852: 1994 using a Tensilon tester (temperature 23°C, tensile speed 10 mm/min, manufacturer: A&D Co., Ltd., product name: TENSILON RTG-1310).
  • the maximum value of the tensile shear stress at this time, the maximum point stress (Tmax) [N/mm 2 ], and the elongation at the maximum stress (Emax) [mm] were measured. In the tensile shear test, if Tmax is 1.4 [N/mm 2 ] or more, the initial shear strength is good, and if Emax is 0.6 [mm] or more, the elongation is good.
  • Test specimens were prepared in the same manner as in the above-mentioned tensile shear test, and were aged for 7 days in an atmosphere having a temperature of 23°C and a relative humidity of 50%. Further, in accordance with JIS K 6861 (1995), the test specimens were subjected to three cycles of cooling at -10°C for 2 hours and then heating at 40°C for 2 hours, and then a tensile shear test was performed. In a thermal cycle test, if Tmax is 1.3 [N/mm 2 ] or more, the shear strength is good, and if Emax is 0.4 [mm] or more, the elongation is good.
  • the strength retention rate is a value calculated by the following formula, and represents the rate of change in maximum stress (Tmax) in a tensile shear test before and after a thermal cycle.
  • Strength retention rate (%) 100 x maximum stress after thermal cycle (Tmax) / maximum stress in tensile shear test (Tmax).
  • Curable compositions were prepared using compositions containing the polymers produced in the above Synthesis Examples and various additives.
  • the additives used are shown below.
  • Examples 1 to 5 are working examples, and Examples 6 to 8 are comparative examples. (Examples 1, 2, 3, 6, 7) Mixtures A-1 to A-3, B-1, and B-2 were prepared so as to have the compositions shown in Table 2.
  • Example 4 Mixture A-1 was prepared so as to have the composition shown in Table 2.
  • 100 parts by mass of ethyl 2-cyanoacrylate, 0.5 parts by mass of hydroquinone, 0.01 parts by mass of methanesulfonic acid, 2 parts by mass of KBM-1003 as a dehydrating agent, and 5 parts by mass of Vamac G as an elastomer were added according to the composition shown in Table 3, and the mixture was stirred at room temperature for 1 hour to completely dissolve the elastomer and ethyl 2-cyanoacrylate, and then 50 parts by mass of the mixture prepared above was added and mixed to obtain a curable composition.
  • the obtained curable compositions were used as the test subjects and the tensile shear test and the thermal cycle test were carried out by the above-mentioned methods. The results are shown in Table 3.
  • Example 5 Mixture A-1 was prepared so as to have the composition shown in Table 2.
  • 100 parts by mass of ethyl 2-cyanoacrylate, 0.5 parts by mass of hydroquinone, 0.01 parts by mass of methanesulfonic acid, 2 parts by mass of KBM-1003 as a dehydrating agent, and 20 parts by mass of Vamac G as an elastomer were added according to the composition shown in Table 3, and the mixture was stirred at room temperature for 12 hours to completely dissolve the elastomer and ethyl 2-cyanoacrylate, and then 50 parts by mass of the mixture prepared above was added and mixed to obtain a curable composition.
  • the obtained curable compositions were used as the test subjects and the tensile shear test and the thermal cycle test were carried out by the above-mentioned methods. The results are shown in Table 3.
  • Example 8 In a glove box under a nitrogen atmosphere, 100 parts by mass of ethyl 2-cyanoacrylate, 0.5 parts by mass of hydroquinone, 0.01 parts by mass of methanesulfonic acid, and 2 parts by mass of a dehydrating agent, KBM-1003, were added according to the formulation shown in Table 3, and the mixture was stirred at room temperature for 10 minutes to obtain a curable composition.
  • the obtained curable compositions were used as the test subjects and the tensile shear test and the thermal cycle test were carried out by the above-mentioned methods. The results are shown in Table 3.
  • the curable composition of the present invention does not gel during the mixing process, and the cured product has good initial shear strength and good shear strength after thermal cycle testing.

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  • Medicinal Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5832677A (ja) * 1981-08-19 1983-02-25 Matsumoto Seiyaku Kogyo Kk 接着剤組成物
JP2005162850A (ja) * 2003-12-02 2005-06-23 Koatsu Gas Kogyo Co Ltd 熱可塑性エラストマー用接着剤
WO2015033738A1 (ja) * 2013-09-03 2015-03-12 東亞合成株式会社 接着剤組成物
WO2017006799A1 (ja) * 2015-07-03 2017-01-12 東亞合成株式会社 接着剤組成物
JP2022020522A (ja) * 2020-07-20 2022-02-01 東亞合成株式会社 硬化性組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5832677A (ja) * 1981-08-19 1983-02-25 Matsumoto Seiyaku Kogyo Kk 接着剤組成物
JP2005162850A (ja) * 2003-12-02 2005-06-23 Koatsu Gas Kogyo Co Ltd 熱可塑性エラストマー用接着剤
WO2015033738A1 (ja) * 2013-09-03 2015-03-12 東亞合成株式会社 接着剤組成物
WO2017006799A1 (ja) * 2015-07-03 2017-01-12 東亞合成株式会社 接着剤組成物
JP2022020522A (ja) * 2020-07-20 2022-02-01 東亞合成株式会社 硬化性組成物

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