WO2018199268A1 - Composition adhésive à base de 2-cyanoacrylate - Google Patents

Composition adhésive à base de 2-cyanoacrylate Download PDF

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Publication number
WO2018199268A1
WO2018199268A1 PCT/JP2018/017089 JP2018017089W WO2018199268A1 WO 2018199268 A1 WO2018199268 A1 WO 2018199268A1 JP 2018017089 W JP2018017089 W JP 2018017089W WO 2018199268 A1 WO2018199268 A1 WO 2018199268A1
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Prior art keywords
block
cyanoacrylate
adhesive composition
acrylate
mass
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PCT/JP2018/017089
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English (en)
Japanese (ja)
Inventor
安藤　勝
裕史 安藤
晃嗣 柴田
河合　道弘
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東亞合成株式会社
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Priority to JP2019514642A priority Critical patent/JP6863456B2/ja
Publication of WO2018199268A1 publication Critical patent/WO2018199268A1/fr

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    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers

Definitions

  • the present invention relates to a 2-cyanoacrylate adhesive composition.
  • the adhesive composition containing a 2-cyanoacrylate compound is polymerized by a weak anion such as a slight amount of water adhering to the adherend surface due to the unique anionic polymerization property of the 2-cyanoacrylate compound as the main component. It is possible to bond various materials firmly in a short time. Therefore, it is used as a so-called instant adhesive in a wide range of fields such as industrial use, medical use, and home use.
  • an adhesive composition containing a 2-cyanoacrylate compound is hard and brittle and does not have a cross-linked structure. Therefore, it has excellent shear bond strength, but it has excellent peel bond strength and impact bond strength. And has a problem that heat resistance is low.
  • methods for blending various modifiers have been proposed.
  • general modifiers are not dissolved in 2-cyanoacrylate compounds, or 2-cyanoacrylate by mixing. Since the compound is anionically polymerized, the modifiers that can be incorporated into the 2-cyanoacrylate compound are limited. Examples of adhesive compositions containing such modifiers include those described in Patent Documents 1 to 3.
  • Patent Document 1 includes a cyanoacrylate monomer (a), a rubbery polymer core, and a glassy polymer shell, wherein the core crosslinking monomer is 0.2 to 4.0% by weight based on the core, and the graft monomer is A cyanoacrylate-based adhesive composition characterized by containing a core-shell polymer (b) in a range of 0.2 to 5.0% by weight based on the core is described.
  • Patent Document 2 discloses (a) a cyanoacrylate component, and (b) a reaction product of a combination of monomers substantially having (a) ethylene, methyl acrylate and a carboxylic acid curing site, and (b) ethylene.
  • Patent Document 3 contains (a) 2-cyanoacrylic acid ester, (b) a polymer having a hydrolyzable silyl group, (c) an elastomer, and (d) an acid catalyst.
  • the content of the components (b), (c) and (d) is 100 parts by mass of the component (a)
  • the component (b) is 5 to 200 parts by mass
  • the component (c) is 5 to 50 parts.
  • An adhesive composition characterized in that the component (d) is 0.0005 to 0.5 parts by mass is described.
  • an adhesive composition containing a conventional 2-cyanoacrylate compound is resistant to repeated thermal changes, particularly between cold and heat cycle resistance, particularly between different types of adherends. It has been found that it has a problem that it is inferior in cold-heat cycle resistance.
  • the present inventors have found that, although the impact resistance is improved by the method described in Patent Document 1, the thermal cycle resistance is not sufficiently satisfactory.
  • the present inventors have found that the elastomer used is non-crosslinkable, and is inferior in heat resistance and heat cycle resistance including a high temperature environment.
  • the problem to be solved by the present invention is to provide a 2-cyanoacrylate-based adhesive composition that is excellent in storage stability and cold-heat cycle resistance after curing.
  • Means for solving the problems include the following aspects.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or —Ph—R 2
  • Ph represents a phenylene group
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms
  • ⁇ 4> The 2-cyano according to any one of ⁇ 1> to ⁇ 3>, wherein the block (a) has at least a structural unit derived from a maleimide compound and a structural unit derived from a styrene compound.
  • ⁇ 5> The 2-cyanoacrylate according to any one of ⁇ 1> to ⁇ 4>, wherein the solubility parameter of the block (a) is 10.0 (cal / cm 3 ) 1/2 or more.
  • ⁇ 6> The 2-cyanoacrylate adhesive composition according to any one of ⁇ 1> to ⁇ 5>, wherein the block (b) is an acrylic polymer block.
  • thermoplastic elastomer (B) has a number average molecular weight of 10,000 to 500,000. object.
  • ⁇ 8> The above ⁇ 1> to ⁇ 7, wherein the content of the thermoplastic elastomer (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the 2-cyanoacrylate compound (A).
  • ⁇ 9> The 2-cyanoacrylate adhesive according to any one of ⁇ 1> to ⁇ 8>, wherein the thermoplastic elastomer (B) is a block copolymer produced by a living radical polymerization method. Composition.
  • thermoplastic elastomer (B) according to any one of ⁇ 1> to ⁇ 9>, wherein the thermoplastic elastomer (B) is a block copolymer produced by a reversible addition-cleavage chain transfer polymerization method. Cyanoacrylate adhesive composition.
  • the 2-cyanoacrylate adhesive composition of the present invention contains a 2-cyanoacrylate compound (A) and a thermoplastic elastomer (B),
  • the thermoplastic elastomer (B) is a block copolymer having a block (a) and a block (b), the glass transition temperature of the block (a) is 80 ° C. or higher, and the block (b) The glass transition temperature is 20 ° C. or lower.
  • the block (a) having a glass transition temperature of 80 ° C. or higher functions as a hard segment
  • the block (b) having a glass transition temperature of 20 ° C. or lower functions as a soft segment. Presumed.
  • thermoplastic elastomer (B) is physically cross-linked in the composition after being cured by the hard segment, so that it has excellent cold-heat cycle resistance and has both a hard segment and a soft segment. It is presumed that the compatibility with the 2-cyanoacrylate compound can be blended without any problem and the storage stability of the adhesive composition containing the 2-cyanoacrylate compound is excellent. Further, the 2-cyanoacrylate adhesive composition of the present invention is excellent in cold and heat cycle resistance after curing even when used for adhesion between different types of adherends (for example, between a metal and a resin). .
  • the adhesive composition of the present invention contains a 2-cyanoacrylate compound (A).
  • a 2-cyanoacrylate compound generally used in this type of adhesive composition can be used without any particular limitation.
  • the 2-cyanoacrylate compounds include methyl, ethyl, chloroethyl, n-propyl, i-propyl, allyl, propargyl, n-butyl, i-butyl, n-pentyl, n-hexyl and cyclohexyl 2-cyanoacrylate.
  • alkyl 2-cyanoacrylate or alkoxyalkyl 2-cyanoacrylate is preferable, and ethyl 2-cyanoacrylate or ethoxyethyl 2-cyanoacrylate is more preferable because of excellent curability.
  • alkyl 2-cyanoacrylate is preferable from the viewpoint of curability and versatility, and alkoxyalkyl 2-cyanoacrylate is preferable from the viewpoint of heat and cold resistance after curing.
  • the 2-cyanoacrylate compound used in the adhesive composition of the present invention may be used alone or in combination of two or more.
  • the content of the 2-cyanoacrylate compound in the adhesive composition of the present invention is preferably 40% by mass or more and 100% by mass or less with respect to the total mass of the adhesive composition from the viewpoint of adhesiveness and curability. 50 mass% or more and 99.9 mass% or less is more preferable, 70 mass% or more and 99.5 mass% or less is further more preferable, and 80 mass% or more and 99.5 mass% or less is particularly preferable. preferable.
  • the block (a) has at least a structural unit represented by the following formula (1) as a structural unit derived from the maleimide compound, from the viewpoints of storage stability and cold-heat cycle resistance after curing. It is more preferable.
  • R 1 represents a hydrogen atom, an alkyl group or an aryl group.
  • substituents examples include a hydroxy group, an alkoxy group, an acetyl group, a halogen atom, an alkyl group, and an aryl group.
  • the aryl group in R 1 of the formula (1) is preferably —Ph—R 2 .
  • Ph represents a phenylene group
  • R 2 represents a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, an acetyl group, or a halogen atom.
  • the styrene compound includes styrene and its derivatives. Specific compounds include styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, vinyl toluene, vinyl xylene, vinyl naphthalene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m- Ethyl styrene, p-ethyl styrene, pn-butyl styrene, p-isobutyl styrene, pt-butyl styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-chloromethyl styrene, p- Examples include chloromethylst
  • a structural unit derived from the styrene compound can be introduced into the block (a).
  • a structural unit derived from the styrene compound can be introduced into the block (a).
  • styrene from the viewpoint of polymerizability, from the group consisting of styrene, ⁇ -methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. At least one selected compound is preferred.
  • the said block (a) has at least the structural unit represented by following formula (2) as a structural unit derived from the said styrene compound from a viewpoint of storage stability and the cold-heat cycle property after hardening. It is preferable.
  • the proportion of the structural unit derived from the styrene compound is 1% by mass to the total mass of the block (a) from the viewpoints of storage stability and cold cycle resistance after curing. It is preferably 70% by mass, more preferably 5% by mass to 70% by mass, still more preferably 10% by mass to 70% by mass, and particularly preferably 20% by mass to 60% by mass. .
  • the proportion of the structural unit derived from the other monomer is 1 mass relative to the total mass of the block (a). % To 50% by mass, preferably 5% to 45% by mass, more preferably 10% to 40% by mass.
  • (meth) acrylic acid alkyl ester compound examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid n.
  • amide group-containing vinyl compounds include (meth) acrylamide, tert-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide.
  • N, N-dimethylaminopropyl (meth) acrylamide and (meth) acrylamide derivatives such as (meth) acryloylmorpholine
  • N-vinylamide series such as N-vinylacetamide, N-vinylformamide and N-vinylisobutyramide Examples include masses.
  • amino group-containing vinyl compound examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
  • Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • Hydroxy group-containing vinyl compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth ) 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, and mono (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol.
  • the solubility parameter of the block (a) (SP value, unless otherwise specified (cal / cm 3 ) 1/2 ) is 10. from the viewpoint of storage stability and oil resistance after curing. It is preferably 0 (cal / cm 3 ) 1/2 or more, more preferably 11.0 (cal / cm 3 ) 1/2 or more, and 12.0 (cal / cm 3 ) 1/2 or more. More preferably.
  • the upper limit of the SP value of the block (a) is not particularly limited, but is preferably 30 (cal / cm 3 ) 1/2 or less.
  • R.D. F It can be calculated by the calculation method described in “Polymer Engineering and Science” 14 (2), 147 (1974) written by Fedors. Specifically, it is based on the calculation method shown in Formula (3).
  • thermoplastic elastomer (B) used in the present invention has at least a block (b) having a glass transition temperature of 20 ° C. or lower.
  • the block (b) is not particularly limited as long as it has a Tg of 20 ° C. or less and can be synthesized, but is compatible with a 2-cyanoacrylate compound, storage stability, and resistance to cold and heat cycles after curing. From this point of view, an acrylic polymer block is preferable.
  • the acrylic polymer block in the present invention is a block containing 50% by mass or more of the structural unit derived from the acrylic compound with respect to the total mass of the block, and the structural unit derived from the acrylic compound is based on the total mass of the block.
  • the acrylic polymer block can be obtained by polymerizing a monomer containing an acrylic monomer.
  • An acrylic monomer refers to an unsaturated compound having an acryloyl group such as acrylic acid and an acrylic ester compound.
  • the acrylate compound include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, and 2-ethylhexyl acrylate.
  • the content of the thermoplastic elastomer (B) in the adhesive composition of the present invention is such that the content of the 2-cyanoacrylate compound (A) is 100 parts by mass from the viewpoint of storage stability and resistance to cold and heat cycle after curing. On the other hand, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more. Moreover, it is preferable that it is 100 mass parts or less from a viewpoint of an adhesion rate, a viscosity, etc.
  • Living radical polymerization may employ any process such as a batch process, a semi-batch process, a dry continuous polymerization process, or a continuous stirred tank process (CSTR).
  • the polymerization method can be applied to various modes such as bulk polymerization without using a solvent, solvent-based solution polymerization, aqueous emulsion polymerization, miniemulsion polymerization or suspension polymerization.
  • RAFT polymerization method reversible addition-cleavage chain transfer polymerization method
  • NMP method nitroxy radical method
  • ATRP method atom transfer radical polymerization method
  • organic tellurium Various polymerization methods such as a polymerization method using a compound (TERP method), a polymerization method using an organic antimony compound (SBRP method), a polymerization method using an organic bismuth compound (BIRP method), and an iodine transfer polymerization method can be employed.
  • the RAFT polymerization method, the NMP method, and the ATRP method are preferable, and the RAFT polymerization method is more preferable from the viewpoint of controllability of polymerization and ease of implementation.
  • the azo compound examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), and the like.
  • the radical polymerization initiator may be used alone or in combination of two or more.
  • a specific alkoxyamine compound having nitroxide or the like is used as a living radical polymerization initiator, and polymerization proceeds via a nitroxide radical derived therefrom.
  • the type of nitroxide radical to be used is not particularly limited, but from the viewpoint of polymerization controllability when polymerizing an acrylate-containing monomer, a compound represented by the formula (4) may be used as the nitroxide compound. preferable.
  • R N1 represents an ethyl group, a methyl group or a hydrogen atom
  • R N2 represents an ethyl group, a methyl group or a nitrile group
  • R N3 represents — (CH 2 ) m —
  • m represents 0 Represents an integer of ⁇ 2
  • R N4 and R N5 each independently represents an alkyl group having 1 to 4 carbon atoms.
  • the nitroxide compound represented by the formula (4) is primarily dissociated by heating at about 70 ° C. to 80 ° C. to cause an addition reaction with the vinyl monomer.
  • a polyfunctional polymerization precursor by adding a nitroxide compound to a vinyl monomer having two or more vinyl groups.
  • the vinyl monomer can be living polymerized by secondary dissociation of the polymerization precursor under heating.
  • the polymerization precursor since the polymerization precursor has two or more active sites in the molecule, a polymer having a narrower molecular weight distribution can be obtained.
  • the usage-amount of a nitroxide compound is suitably adjusted with the kind etc. of the monomer to be used and a nitroxide compound.
  • the nitroxide radical represented by the formula (5) ranges from 0.001 mol to 0.2 mol with respect to 1 mol of the nitroxide compound represented by the formula (4).
  • the polymerization may be carried out by adding in the above.
  • R N4 and R N5 each independently represent an alkyl group having 1 to 4 carbon atoms.
  • Addition of 0.001 mol or more of the nitroxide radical represented by the formula (5) shortens the time for the concentration of the nitroxide radical to reach a steady state. As a result, the polymerization can be controlled to a higher degree, and a polymer with a narrower molecular weight distribution can be obtained. On the other hand, if the amount of the nitroxide radical added is too large, the polymerization may not proceed.
  • a more preferable addition amount of the nitroxide radical with respect to 1 mol of the nitroxide compound is in a range of 0.01 mol to 0.5 mol, and a more preferable addition amount is in a range of 0.05 mol to 0.2 mol.
  • the reaction temperature in the NMP method is preferably 50 ° C. to 140 ° C., more preferably 60 ° C. to 130 ° C., further preferably 70 ° C. to 120 ° C., and more preferably 80 ° C. to 120 ° C. Is particularly preferred. If reaction temperature is 50 degreeC or more, a polymerization reaction can be advanced smoothly. On the other hand, if the reaction temperature is 140 ° C. or lower, side reactions such as radical chain transfer tend to be suppressed.
  • an A- (BA) n- type structure such as an ABA triblock copolymer comprising block (a) -block (b) -block (a) is obtained by living radical polymerization, each block is polymerized sequentially.
  • the target block copolymer may be obtained, but it is preferable that the target block copolymer is obtained more efficiently when it is produced by a method including the following two-stage polymerization process.
  • a known polymerization solvent can be used in living radical polymerization.
  • aromatic compounds such as benzene, toluene, xylene and anisole
  • ester compounds such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate
  • ketone compounds such as acetone and methyl ethyl ketone
  • dimethylformamide, acetonitrile, dimethyl sulfoxide Examples include alcohol and water.
  • Stabilizers include (1) aliphatic sulfonic acids such as sulfur dioxide and methanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, trifluoride such as boron trifluoride methanol and boron trifluoride diethyl ether.
  • examples include anionic polymerization inhibitors such as boron complexes, HBF 4 , and trialkyl borates, and (2) radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, catechol, and pyrogallol. These stabilizers may be used alone or in combination of two or more.
  • Any curing accelerator can be used as long as it promotes anionic polymerization of the 2-cyanoacrylate adhesive composition.
  • the curing accelerator include polyether compounds, calixarenes, thiacalixallenes, pyrogallol allenes, and onium salts. These curing accelerators may be used alone or in combination of two or more.
  • Plasticizers include triethyl acetyl citrate, tributyl acetyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, phthalate Diheptyl acid, 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, trigly
  • tributyl acetyl citrate dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate, and dipropylene glycol diethylene glycol are preferred because of their good compatibility with 2-cyanoacrylate compounds and high plasticization efficiency. Benzoate is preferred.
  • plasticizers may be used alone or in combination of two or more.
  • the particles that may be blended in the adhesive composition are for adjusting the thickness of the adhesive layer when the adhesive composition is used.
  • the average particle diameter of the particles is preferably 10 ⁇ m to 200 ⁇ m, more preferably 15 ⁇ m to 200 ⁇ m, and still more preferably 15 ⁇ m to 150 ⁇ m.
  • the material of the particles is not particularly limited as long as it is insoluble in the 2-cyanoacrylate compound used and does not cause alteration such as polymerization.
  • the content of the particles is not particularly limited, but when the content of the 2-cyanoacrylate compound is 100 parts by mass, it is preferably 0.1 parts by mass to 10 parts by mass, and 1 part by mass to 5 parts by mass. More preferably, it is more preferably 1 part by weight to 3 parts by weight. When the content is in the range of 0.1 to 10 parts by mass, the influence on the curing rate and the adhesive strength can be reduced.
  • the average particle diameter of the particles in the present invention is a volume-based average value measured by a laser diffraction particle size distribution measuring apparatus.
  • composition ratio of polymer> The composition ratio of the obtained polymer was identified or calculated from 1 H-NMR measurement.
  • the heat flux curve shows that about 10 mg of a sample was cooled to ⁇ 50 ° C. and held for 5 minutes, then heated to 300 ° C. at 10 ° C./min, subsequently cooled to ⁇ 50 ° C. and held for 5 minutes, then 10 ° C. / It was obtained under conditions where the temperature was raised to 350 ° C. in min.
  • Tg of polymer block (b) was used as a sample for the Tg of the acrylic polymer block (b). Moreover, Tg of polymer block (a) is obtained (with Tg of acrylic polymer block (b)) by using the block copolymers obtained in Examples and Comparative Examples as samples.
  • the polymer solution obtained by stopping the reaction was purified by reprecipitation from hexane and dried in vacuo.
  • the molecular weight of the obtained polymer 1 was Mn72,100, Mw78,600, and Mw / Mn was 1.09 from GPC (gel permeation chromatography) measurement (polystyrene conversion).
  • a block copolymer A was obtained by reprecipitation purification from methanol and vacuum drying of the polymerization solution which stopped the reaction.
  • Mn86,500, Mw124,000, and Mw / Mn were 1.43.
  • Example 2 and 3 and Comparative Examples 1 to 3 An adhesive composition was produced in the same manner as in Example 1 except that the block copolymer A was changed to the compounding agents shown in Table 4.
  • Example 4 Ethoxyethyl 2-cyanoacrylate was blended with 20 ppm sulfur dioxide and 1,000 ppm hydroquinone to obtain an ethoxyethyl 2-cyanoacrylate blend. Next, 20 parts of the block copolymer A (100 parts of the ethoxyethyl 2-cyanoacrylate compound was added) were mixed and stirred overnight at 23 ° C., and dissolved to prepare an adhesive composition.
  • Example 5 An adhesive composition was produced in the same manner as in Example 4 except that the block copolymer A was changed to the compounding agents shown in Table 5.
  • Vamac Thermoplastic elastomer, manufactured by DuPont Elastomer, trade name “Vacac G”, ethylene / methyl acrylate / acrylic acid random copolymer
  • Example 10 to 14 and Comparative Examples 6 to 8 An adhesive composition was produced in the same manner as in Example 9, except that the type of 2-cyanoacrylate, the type of block copolymer, and the blending amount thereof were changed to those shown in Table 6.
  • Examples 4 to 8 showed a retention of 50% or more even in a cooling cycle test in a wider temperature range, and were excellent in the storage stability of the adhesive composition. .
  • Comparative Example 4 was peeled off during the cold cycle test.
  • Comparative Example 5 was not peeled off in the cooling and heating cycle test, the strength after the test was significantly reduced.
  • Examples 9 to 14 had high initial tensile shear adhesive strength and tensile shear adhesive strength after the thermal cycle, and were excellent in storage stability of the adhesive composition.
  • Comparative Examples 6 and 8 were peeled off during the cooling / heating cycle test. Although the comparative example 7 was not peeled off in the thermal cycle test, the strength after the test was significantly reduced.
  • the adhesive composition of the present invention contains a 2-cyanoacrylate compound and can be used as a so-called instantaneous adhesive in a wide range of products and technical fields such as general households and medical fields, as well as various industries. it can. In particular, it is useful for bonding automobile parts, electrical parts, electronic parts, and various footwear.
  • the adhesive composition of the present invention can be suitably used for adhesion between different types of adherends (for example, between a metal and a resin).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Cette composition adhésive à base de 2-cyanoacrylate contient un composé à base de 2-cyanoacrylate (A) et un élastomère thermoplastique (B), l'élastomère thermoplastique (B) étant un copolymère séquencé présentant un bloc (a) et un bloc (b) et la température de transition vitreuse du bloc (a) étant de 80°C ou plus et la température de transition vitreuse du bloc (b) étant de 20°C ou moins.
PCT/JP2018/017089 2017-04-26 2018-04-26 Composition adhésive à base de 2-cyanoacrylate WO2018199268A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020128349A1 (fr) * 2018-12-19 2020-06-25 Arkema France Composition comprenant des cyanoacrylates et au moins un copolymere a blocs
WO2022070868A1 (fr) * 2020-09-29 2022-04-07 旭化成株式会社 Épaississant pour adhésif à base de cyanoacrylate

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JPS5330642A (en) * 1976-07-14 1978-03-23 Loctite Ireland Ltd Composition of thixotropy *pseudoliquidity* hardening adhesive
JPS5974176A (ja) * 1982-10-20 1984-04-26 Yugo Suzuki 接着剤組成物
JPH06271817A (ja) * 1993-03-23 1994-09-27 Three Bond Co Ltd α−シアノアクリレート系接着剤組成物及びその製造方法
JPH09143431A (ja) * 1995-11-22 1997-06-03 Nippon Zeon Co Ltd 紫外線硬化性組成物、それを用いた接着方法、および接着物
JP2011231210A (ja) * 2010-04-27 2011-11-17 Toagosei Co Ltd 接着方法
WO2017073287A1 (fr) * 2015-10-27 2017-05-04 東亞合成株式会社 Polymère séquencé, son procédé de production et son utilisation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5330642A (en) * 1976-07-14 1978-03-23 Loctite Ireland Ltd Composition of thixotropy *pseudoliquidity* hardening adhesive
JPS5974176A (ja) * 1982-10-20 1984-04-26 Yugo Suzuki 接着剤組成物
JPH06271817A (ja) * 1993-03-23 1994-09-27 Three Bond Co Ltd α−シアノアクリレート系接着剤組成物及びその製造方法
JPH09143431A (ja) * 1995-11-22 1997-06-03 Nippon Zeon Co Ltd 紫外線硬化性組成物、それを用いた接着方法、および接着物
JP2011231210A (ja) * 2010-04-27 2011-11-17 Toagosei Co Ltd 接着方法
WO2017073287A1 (fr) * 2015-10-27 2017-05-04 東亞合成株式会社 Polymère séquencé, son procédé de production et son utilisation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020128349A1 (fr) * 2018-12-19 2020-06-25 Arkema France Composition comprenant des cyanoacrylates et au moins un copolymere a blocs
FR3090666A1 (fr) * 2018-12-19 2020-06-26 Arkema France Composition comprenant des cyanoacrylates et au moins un copolymère à blocs
WO2022070868A1 (fr) * 2020-09-29 2022-04-07 旭化成株式会社 Épaississant pour adhésif à base de cyanoacrylate
JPWO2022070868A1 (fr) * 2020-09-29 2022-04-07
JP7353727B2 (ja) 2020-09-29 2023-10-02 旭化成株式会社 シアノアクリレート系接着剤用増粘剤

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