WO2024210092A1 - 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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WO2024210092A1
WO2024210092A1 PCT/JP2024/013457 JP2024013457W WO2024210092A1 WO 2024210092 A1 WO2024210092 A1 WO 2024210092A1 JP 2024013457 W JP2024013457 W JP 2024013457W WO 2024210092 A1 WO2024210092 A1 WO 2024210092A1
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group
curable composition
polymer
groups
reactive silicon
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French (fr)
Japanese (ja)
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旭卉 リュウ
吉 竹田
高 伊藤
佳孝 砂山
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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.
  • 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 a 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.
  • An object of the present invention is to provide a curable composition which provides a cured product having high initial shear strength and good shear strength and elongation after a thermal cycle test.
  • the present invention is based on the discovery that by using a specific oxyalkylene polymer having four or more terminal groups per molecule and a reactive silicon group as the polymer to be combined with a 2-cyanoacrylic acid ester, a curable composition can be obtained in which the initial shear strength of the cured product is high and which has good elongation and strength in a thermal cycle test. Furthermore, it is possible to obtain a cured product even without blending an elastomer, and the cured product has good initial shear strength and good shear strength in 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 four or more end groups in one molecule, and the four or more end groups may be different from each other.
  • the curable composition wherein the terminal group contains a reactive silicon group represented by the following formula (1): -SiR a X 3-a formula (1)
  • 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 3.0 to 50.0 reactive silicon groups per molecule, more preferably 4.0 to 50.0 reactive silicon groups, and even more preferably 5.0 to 50.0 reactive silicon groups.
  • the oxyalkylene polymer is obtained by reacting a precursor polymer having at least four hydroxyl groups with a silylating agent having a reactive silicon group,
  • the curable composition according to any one of [1] to [3], 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 a divalent linking group
  • 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 4 or more
  • at least four Si 10 are reactive silicon groups
  • 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 [7].
  • the curable composition further comprises an elastomer, The curable composition according to any one of [1] to [8], wherein the content of the elastomer is 0 to 20 parts by mass relative to 100 parts by mass of the 2-cyanoacrylic acid ester.
  • the curable composition further comprises an elastomer, The ratio of the elastomer to the total mass of the curable composition is preferably 1 to 50 mass%, more preferably 2 to 45 mass%, and still more preferably 4 to 40 mass%.
  • the curable composition according to any one of [1] to [9].
  • the curable composition further comprises an acid catalyst,
  • the ratio of the acid catalyst to the total mass of the curable composition is preferably 0.001 to 5 mass%, more preferably 0.005 to 1 mass%, and even more preferably 0.008 to 0.1 mass%.
  • the curable composition according to any one of [1] to [10].
  • the polymer is obtained by reacting a precursor polymer having at least four 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 four hydroxyl groups; more preferably a polymer obtained by ring-opening addition polymerization of ethylene oxide or propylene oxide and a tetrahydric polyhydric alcohol, a pentahydric polyhydric alcohol, a hexahydric polyhydric alcohol, a heptahydric or higher polyhydric alcohol, or a polyglycerol having 50 or less functional groups; or more preferably a polymer obtained by ring-opening addition polymerization of ethylene oxide or propylene oxide and 1,2,3,4-butanetetraol, pentaerythritol, diglycerol, sorbitan, ribose, arabinose,
  • the curable composition of the present invention can give a cured product that has high initial shear strength and exhibits good shear strength and elongation in a thermal cycle test. Furthermore, even in the case of a curable composition that does not contain an elastomer, the initial shear strength of the cured product and the shear strength in a thermal cycle test are good.
  • 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 four or more active hydrogens as described above.
  • the number average molecular weight (hereinafter, referred to as "Mn”) and the mass 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 invention is a curable composition containing a 2-cyanoacrylic acid ester and a polymer A
  • the polymer A is a curable composition having four or more terminal groups in one molecule and a reactive silicon group represented by the following formula (1), and the terminal group has the reactive silicon group, an unsaturated group, or a hydroxyl group.
  • -SiR a X 3-a formula (1) [In formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and 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.]
  • the 2-cyanoacrylic acid ester of the present invention may be any 2-cyanoacrylic acid ester that is generally used in a curable composition, 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 10 include 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 meth
  • the polymer A of the present invention is an oxyalkylene polymer having four or more terminal groups in one molecule and having a reactive silicon group represented by the formula (1), and the terminal group has the reactive silicon group, an unsaturated group, or a hydroxyl group.
  • the polymer A in the curable composition of the present invention may contain two or more types of polymers.
  • 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 the 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.
  • X may be the same or different.
  • 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 trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, methyldimethoxysilyl, methyldiethoxysilyl, ethyldimethoxysilyl, methyldiisopropoxysilyl, ( ⁇ -chloromethyl)dimethoxysilyl, and ( ⁇ -chloromethyl)diethoxysilyl.
  • trimethoxysilyl In terms of high activity and good curing properties, trimethoxysilyl, triethoxysilyl, methyldimethoxysilyl, and methyldiethoxysilyl are preferred, with methyldimethoxysilyl and trimethoxysilyl being more preferred.
  • 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.
  • polyoxyalkylene chain of polymer A examples include polyoxypropylene chain, polyoxyethylene chain, poly(oxy-2-ethylethylene) chain, poly(oxy-1,2-dimethylethylene) chain, poly(oxytetramethylene) chain, poly(oxyethylene-oxypropylene) chain, and poly(oxypropylene-oxy-2-ethylethylene) chain.
  • Polyoxypropylene chain and poly(oxyethylene-oxypropylene) chain are preferred, and polyoxypropylene chain is more preferred.
  • 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 a divalent linking group;
  • 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 4 or more; and at least four Si 10 are reactive silicon groups.
  • n is preferably 4 or more and 50 or less, more preferably 5 or more and 20 or less, and even more preferably 6 or more and 10 or less.
  • the polymer A has 4 or more end groups. From the viewpoint of improving the initial shear strength and elongation in a thermal cycle test and in a cured product of the curable composition, the number of end groups of the polymer A is 4 or more, more preferably 5 or more, and even more preferably 6 or more, and is preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less.
  • 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 3.0, more preferably 1.0 to 2.5, and even more preferably 1.0 to 2.0, 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 3.0 reactive silicon groups, more preferably 0.3 to 2.0 reactive silicon groups, and even more preferably 0.4 to 1.0 reactive silicon groups.
  • Polymer A preferably has an average of 3.0 or more reactive silicon groups per molecule, more preferably 4.0 or more, and even more preferably 5.0 or more reactive silicon groups, and preferably 50.0 or less, more preferably 20.0 or less, even more preferably 15.0 or less, and particularly preferably 10.0 or less reactive silicon groups.
  • the terminal group in polymer A may contain a group represented by the following formula (2) or the following formula (3):
  • X 1 in the following formula (3) is a monovalent group represented by any one of the following formulas (4) to (7).
  • Si 1 represents the reactive silicon group represented by the above formula (1). When multiple Si 1s are present in one terminal group, they may be the same or different from each other.
  • R 1 and R 3 each independently represent a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to the carbon atom in the linking group is a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • R 1 is preferably —CH 2 —O—CH 2 —, —CH 2 O— or —CH 2 —, and more preferably —CH 2 —O—CH 2 —.
  • R 3 is preferably —CH 2 — or —C 2 H 4 —, and more preferably —CH 2 —.
  • R 2 and R 4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • the hydrocarbon group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • Examples of the straight-chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • branched alkyl groups include an isopropyl group, an s-butyl group, a t-butyl group, a 2-methylbutyl group, a 2-ethylbutyl group, a 2-propylbutyl group, a 3-methylbutyl group, a 3-ethylbutyl group, a 3-propylbutyl group, a 2-methylpentyl group, a 2-ethylpentyl group, a 2-propylpentyl group, a 3-methylpentyl group, a 3-ethylpentyl group, a 3-propylpentyl group, a 4-methylpentyl group, a 4-ethylpentyl group, a 4-propylpentyl group, a 2-methylhexyl group, a 2-ethylhexyl group, a 2-propylhexyl group, a 3-methylhexyl group, a 3-e
  • n represents an integer of 1 to 10, preferably 1 to 7, more preferably 1 to 5, and even more preferably 1.
  • R5 represents a single bond or a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to the carbon atom in the linking group is a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • Examples of the divalent linking group in R5 are the same as the examples of the divalent linking group in R1 and R3 .
  • R 5 is preferably a single bond or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 3 carbon atoms, and further preferably a single bond or a methylene group.
  • R6 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • Examples of the monovalent hydrocarbon group in R6 are the same as the examples of the monovalent hydrocarbon group in R2 and R4 .
  • R6 is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
  • R 7 and R 8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms.
  • the hydrocarbon group is preferably a linear or branched alkyl group having a carbon number of 1 to 9.
  • Examples of the alkyl group as R 7 and R 8 are the same as the examples of the alkyl group as R 2 and R 4 . It is preferable that R 7 and R 8 are both hydrogen atoms.
  • 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 represented by the following formula (i) (hereinafter also referred to as "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.
  • -C( O)NH-
  • the group (i) is a divalent group derived from an isocyanate group contained in the compound 1. When the compound 1 contains one isocyanate group, the organic group A contains one group (i).
  • 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 (8).
  • the Mn of polymer A is preferably 5,000 to 300,000, more preferably 10,000 to 200,000, even more preferably 20,000 to 100,000, and particularly preferably 30,000 to 70,000. If it is within the above 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 8.00 or less. Since good elongation properties are easily obtained, a smaller molecular weight distribution is preferable, 1.00 to 8.00 is more preferable, and 1.00 to 1.40 is even more preferable.
  • the silylation rate of the polymer A is preferably from 25 to 100 mol %, more preferably from 30 to 98 mol %, and further preferably from 50 to 98 mol %.
  • the average silylation rate of the entire polymer A falls within the above range.
  • Polymer A can be obtained by introducing the reactive silicon group into the terminal group of a precursor polymer, which 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 5,000 to 300,000, more preferably 10,000 to 200,000, even more preferably 20,000 to 100,000, and particularly preferably 30,000 to 70,000. If it is 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.
  • the initiator preferably has 4 or more active hydrogen-containing groups as a lower limit, more preferably 5 or more, and even more preferably 6 or more active hydrogen-containing groups.
  • the upper limit is preferably 50 or less, more preferably 45 or less, and even more preferably 10 or less active hydrogen-containing groups.
  • the active hydrogen-containing group in the initiator is preferably a hydroxyl group.
  • initiators having 4 to 50 active hydrogen-containing groups include tetrahydric polyhydric alcohols such as 1,2,3,4-butanetetraol, pentaerythritol, diglycerin, sorbitan, ribose, arabinose, xylose, and lyxose; pentahydric polyhydric alcohols such as triglycerin, arabitol, xylitol, glucose, fructose, galactose, mannose, allose, gulose, idose, talose, and quercitol; dipentaerythritol, sorbitol Examples include hexavalent polyhydric alcohols such as galactitol, mannitol, allitol, iditol, talitol, and inositol; heptavalent or higher polyhydric alcohols such as disaccharides (sucrose, etc.), polysaccharides (a
  • 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.
  • Method (c) A method in which the hydroxyl groups of the precursor polymer are converted to groups having an isocyanate group, and then a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula (1) is reacted with the hydroxyl groups to convert them to groups having a reactive silicon group represented by formula (1).
  • a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula (1) is reacted with the hydroxyl groups to convert them to groups having a reactive silicon group represented by formula (1).
  • Method (d) A method in which more than one unsaturated group is introduced into one terminal group of the precursor polymer, and then the unsaturated group is reacted with a silylating agent.
  • a conventionally known method can be used, such as the methods proposed in JP-B-45-36319, JP-A-50-156599, JP-A-61-197631, JP-A-03-72527, JP-A-08-231707, JP-A-2011-178955, U.S. Patent No. 3,632,557, and U.S. Patent No. 4,960,844.
  • Examples of the silylating agent in the method (a) include compounds having both a group capable of reacting with an unsaturated group to form a bond (e.g., a sulfanyl group) and the reactive silicon group, and hydrosilane compounds (e.g., HSiR a X 3-a , where R, X, and a are the same as those in formula (1)).
  • a group capable of reacting with an unsaturated group to form a bond e.g., a sulfanyl group
  • hydrosilane compounds e.g., HSiR a X 3-a , where R, X, and a are the same as those in formula (1).
  • trimethoxysilane triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, methyldiisopropoxysilane, ( ⁇ -chloromethyl)dimethoxysilane, ( ⁇ -chloromethyl)diethoxysilane, and 3-mercaptopropyltrimethoxysilane.
  • trimethoxysilane, triethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferred, and methyldimethoxysilane or trimethoxysilane is more preferred.
  • the compound 1 to be reacted with the precursor polymer in the method (b) is represented by the following formula (8).
  • 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 method (b) 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 obtained 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 active hydrogens 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 (9) 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 (10), but the present invention is not limited thereto.
  • R 10 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 11 is a divalent organic group
  • -SiR a X 3-a is the above-mentioned This is the same as equation (1).
  • the urethane bond and the reactive silicon group-containing group have two urethane bonds.
  • R 10 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 formula (9) 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 11 in the silylating agent having a functional group capable of reacting with an isocyanate group represented by formula (10) and -SiR a X 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.
  • a conventionally known method can be used, for example, the methods described in WO 2013/180203, WO 2014/192842, JP 2015-105293, JP 2015-105322, JP 2015-105323, JP 2015-105324, WO 2015/080067, WO 2015/105122, WO 2015/111577, WO 2016/002907, JP 2016-216633, and JP 2017-39782.
  • the preferred method for introducing more than 1.0 unsaturated group per terminal group into the terminal group of the precursor polymer is to react an alkali metal salt with the precursor polymer, then react with an epoxy compound having an unsaturated group, and then react with a halogenated hydrocarbon compound having an unsaturated group, or to react an alkali metal salt with the precursor polymer, then react with a halogenated hydrocarbon compound having a carbon-carbon triple bond.
  • alkali metal salt examples include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoints of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, and sodium methoxide and potassium ethoxide are more preferred. From the viewpoint of availability, sodium methoxide is particularly preferred.
  • the alkali metal salt may be used in a state dissolved in a solvent.
  • epoxy compounds having an unsaturated group examples include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide. Allyl glycidyl ether is preferred.
  • an epoxy compound having an unsaturated group a compound represented by the following formula (11) is preferred.
  • R 1 and R 2 are the same as R 1 and R 2 in formula (2) above.
  • halogenated hydrocarbon compound having an unsaturated group one or both of a halogenated hydrocarbon compound containing a carbon-carbon double bond and a halogenated hydrocarbon compound containing a carbon-carbon triple bond can be used.
  • halogenated hydrocarbon compounds containing a carbon-carbon double bond include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred.
  • halogenated hydrocarbon compounds containing a carbon-carbon triple bond examples include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo-
  • the iodine examples include 2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2
  • the above reaction results in a derivative having more than 1.0 unsaturated group per one end group of the precursor polymer.
  • the derivative of the precursor polymer may contain unreacted active hydrogen-containing groups at the end groups.
  • the number of active hydrogen-containing groups contained in the derivative of the precursor polymer is preferably 0.3 or less, and more preferably 0.1 or less, per molecule from the viewpoint of storage stability.
  • the unsaturated group of the precursor polymer derivative is reacted with a silylating agent to introduce a reactive silicon group into the terminal group to obtain polymer A.
  • a silylating agent examples include the same ones as those mentioned above.
  • 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%, and even more preferably 4 to 40 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, 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 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 " 1 H-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 ester.
  • 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.
  • the copolymer for example, ethylene/methyl acrylate copolymer, ethylene/methyl acrylate/butyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/vinyl acetate copolymer, butadiene/methyl acrylate copolymer, butadiene/acrylonitrile copolymer, butadiene/acrylonitrile/acrylic acid ester copolymer, and butadiene/styrene/acrylonitrile/methyl acrylate copolymer can be used.
  • ethylene/methyl acrylate copolymer and ethylene/methyl acrylate/butyl acrylate copolymer are particularly preferable.
  • a copolymer obtained by polymerizing a monomer used in each of the above copolymers with a carboxyl group-containing monomer such as acrylic acid and/or methacrylic acid can also be used.
  • These copolymers may be used alone or in combination of two or more kinds, 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 of the present invention does not contain an elastomer, or if it does contain an elastomer, it contains a small amount of it.
  • the content of the elastomer is preferably 0.1 to 20 parts by mass, assuming that the 2-cyanoacrylic acid ester is 100 parts by mass.
  • the content of the elastomer depends on the types of the 2-cyanoacrylic acid ester and polymer A, but is more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass. It is particularly preferably 0.7 to 4 parts by mass. If the content of the elastomer component is within the above range, the 2-cyanoacrylic acid ester and polymer A can be stably compatible with each other, and as a result, a curable composition having excellent adhesive function can be obtained.
  • 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 of the present invention 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 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 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.
  • a 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 a 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 more 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 2-cyanoacrylic acid ester, particularly when the copolymer has a large number of poorly soluble segments, and the retention of adhesive strength in a thermal cycle 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 of 500 nm or less, particularly 1 to 200 nm), which is produced, for example, from silicon tetrachloride as a raw material by oxidation in a gas phase in a high-temperature flame.
  • 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 capable of forming 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)
  • hydrophilic silica it is preferable to use hydrophilic silica in combination
  • a copolymer containing a large amount of monomers capable of forming a poorly soluble polymer that is, a copolymer containing a large amount of poorly soluble segments, is used, 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 of the present invention.
  • the cured product can be produced by curing the curable composition with moisture in the air.
  • the cured product of the present invention 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 2.5 [N/mm 2 ] or more can be achieved.
  • a Tmax of 2.0 [N/ mm2 ] or more and an elongation at maximum stress (Emax) of 1.25 [mm] or more can be achieved, or in a thermal cycle test (2) described below, a Tmax of 2.0 [N/ mm2 ] or more and an Emax of 1.0 [mm] or more can be achieved.
  • the maximum stress (Tmax) measured in a tensile shear test described later is preferably 2.5 [N/mm 2 ] or more, more preferably 3.2 [N/mm 2 ] or more, and even more preferably 4.0 [N/mm 2 ] or more.
  • the Tmax measured in a thermal cycle test (1) described later is preferably 2.0 [N/mm 2 ] or more, more preferably 3.0 [N/mm 2 ] or more, and even more preferably 3.5 [N/mm 2 ] or more.
  • the elongation at maximum stress (Emax) measured in a thermal cycle test (1) described later is preferably 1.25 mm or more, more preferably 1.50 mm or more and even more preferably 2.00 mm or more.
  • the Tmax measured in a thermal cycle test (2) described later is preferably 2.0 [N/mm 2 ] or more, more preferably 2.5 [N/mm 2 ] or more, and even more preferably 3.0 [N/mm 2 ] or more.
  • the elongation at maximum stress (Emax) measured in a thermal cycle test (2) described later is preferably 1.25 mm or more, more preferably 1.50 mm or more, and even more preferably 2.00 mm or more.
  • the difference between Tmax measured in the thermal cycle test (1) described later and Tmax measured in the thermal cycle test (2) described later, expressed as [Tmax measured in the thermal cycle test (1)] - [Tmax measured in the thermal cycle test (2)], is preferably 0 to 5.0 [N/mm 2 ], more preferably 0 to 2.0 [N/mm 2 ], and even more preferably 0 to 0.1 [N/mm 2 ].
  • the difference between the elongation at maximum stress (Emax) measured in a thermal cycle test (1) described later and the elongation at maximum stress (Emax) measured in a thermal cycle test (2) described later, expressed as [elongation at maximum stress (Emax) measured in a thermal cycle test (1)] - [elongation at maximum stress (Emax) measured in a thermal cycle test (2)], is preferably 0 to 2.00 [mm], more preferably 0 to 1.50 [mm], and even more preferably 0 to 1.00 [mm].
  • the curable composition of the present invention is suitable for use as an adhesive.
  • it can be used as an 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 of the present invention comprises a cured product obtained by curing the curable composition of the present invention 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 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 2.5 [N/mm 2 ] or more, the initial shear strength is good, and if Emax is 1.5 [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, the test specimens were subjected to 10 cycles of cooling at -40°C for 1 hour and then heating at 80°C for 1 hour, and then the tensile shear test was performed. In the thermal cycle test (1), when Tmax is 2.0 [N/mm 2 ] or more, the shear strength is good, and when Emax is 1.25 [mm] or more, the elongation is good.
  • Example 2 A test specimen was prepared in the same manner as in the above-mentioned tensile shear test, and was 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 specimen was 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 the thermal cycle test (2), when Tmax is 2.0 [N/mm 2 ] or more, the shear strength is good, and when Emax is 1.0 [mm] or more, the elongation is good.
  • the number of terminal groups, reactive silicon group structure, hydroxyl value-based molecular weight, Mn, Mw/Mn, silylation rate, and number of reactive silicon groups per molecule of the obtained Polymer A-1 are shown in Table 1.
  • the polymers obtained in the following synthesis examples are also shown in Table 1.
  • precursor polymer a-3 propylene oxide was polymerized to obtain an oxypropylene polymer (precursor polymer a-3).
  • the hydroxyl value-based molecular weight of the precursor polymer was 180,000.
  • 0.97 molar equivalents of 3-isocyanatepropyltrimethoxysilane was added relative to the hydroxyl groups of the precursor polymer, and dioctyltin bisisooctylthioglycol (Neostan U-860: product name of Nitto Kasei Co., Ltd.) was added as a catalyst.
  • the temperature was raised to 80°C, and stirring was continued while maintaining the temperature at 80°C.
  • Curable compositions were prepared using compositions containing the polymers produced in the above Synthesis Examples and various additives.
  • the additives used are shown below.
  • the curable composition was prepared without an elastomer.
  • Mixtures A-1 to A-3 and B-1 were prepared so as to have the compositions 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, and 2 parts by mass of a dehydrating agent, KBM-1003 were added according to the compositions shown in Table 4, and the mixture was stirred at room temperature for 10 minutes to completely dissolve the mixture, 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 (2) were carried out by the above-mentioned methods. The results are shown in Table 4.
  • curable compositions that have already been produced or will be produced in the future can also achieve the same effects by producing them based on common technical knowledge in the same way as in the above examples.
  • the precursor polymers of polymer A having different numbers of terminal groups may be produced by polymerizing an initiator having 4 to 50 active hydrogen-containing groups and a cyclic ether having an epoxy group, or may be obtained as a commercially available product.
  • the polymer A produced by using the precursor polymer according to the above-mentioned methods (a) to (d) may be used.
  • compositions containing hydroquinone as a polymerization inhibitor are described, but this may be replaced with (1) boron trifluoride complexes such as boron trifluoride methanol and boron trifluoride diethyl ether, HBF4, and anionic polymerization inhibitors such as trialkyl borates, or (2) radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, catechol, and pyrogallol.
  • boron trifluoride complexes such as boron trifluoride methanol and boron trifluoride diethyl ether, HBF4, and anionic polymerization inhibitors such as trialkyl borates
  • radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, catechol, and pyrogallol.
  • compositions containing methanesulfonic acid as the acid catalyst are described, but the acid catalyst may be replaced with 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.
  • compositions containing vinyltrimethoxysilane as a dehydrating agent are described, but this may be replaced with acrylsilanes such as ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, ⁇ -acryloxypropylmethyldimethoxysilane, and ⁇ -acryloxypropylmethyldiethoxysilane; mercaptosilanes such as ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane; ⁇ -ureidopropyltriethoxysilane; and methyltrimethoxysilane.
  • acrylsilanes such as ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, ⁇ -acryloxypropylmethyldimethoxysilane, and ⁇ -acryloxypropylmethyldiethoxysilane
  • the curable composition of the present invention can give a cured product that has high initial shear strength and exhibits good shear strength and elongation in a thermal cycle test. Furthermore, even in the case of a curable composition that does not contain an elastomer, the initial shear strength of the cured product and the shear strength in a thermal cycle test are good.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03265676A (ja) * 1990-03-15 1991-11-26 Taoka Chem Co Ltd α―シアノアクリレート接着剤用プライマー及びそれを用いる接着方法
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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03265676A (ja) * 1990-03-15 1991-11-26 Taoka Chem Co Ltd α―シアノアクリレート接着剤用プライマー及びそれを用いる接着方法
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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