WO2023286709A1 - Composition d'adhésif à base de 2-cyanoacrylate - Google Patents

Composition d'adhésif à base de 2-cyanoacrylate Download PDF

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Publication number
WO2023286709A1
WO2023286709A1 PCT/JP2022/027096 JP2022027096W WO2023286709A1 WO 2023286709 A1 WO2023286709 A1 WO 2023286709A1 JP 2022027096 W JP2022027096 W JP 2022027096W WO 2023286709 A1 WO2023286709 A1 WO 2023286709A1
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Prior art keywords
cyanoacrylate
adhesive composition
recovery rate
elongation recovery
compound
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PCT/JP2022/027096
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English (en)
Japanese (ja)
Inventor
絵利香 一色
謙一 石▲崎▼
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東亞合成株式会社
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Priority to JP2023534774A priority Critical patent/JPWO2023286709A1/ja
Publication of WO2023286709A1 publication Critical patent/WO2023286709A1/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
    • 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 disclosure relates to a 2-cyanoacrylate adhesive composition.
  • An adhesive composition containing a 2-cyanoacrylate compound initiates polymerization due to a weak anion such as a slight amount of moisture adhering to the surface of an adherend due to the unique anionic polymerizability of the 2-cyanoacrylate compound. Materials can be firmly joined in a short time. Therefore, it is used as a so-called instant adhesive in a wide range of fields such as industrial, medical and household use.
  • Japanese Patent No. 5267571 discloses a 2-cyanoacrylate ester and a polyfunctional cyanoacrylate ester having two or more 2-cyanoacryloyl groups.
  • the number average molecular weight of the (b) polyfunctional cyanoacrylic acid ester is 1,000 to 50,000 and the 2-cyanoacrylic acid ester is 100 parts by mass.
  • the (b) polyfunctional cyanoacrylic acid ester is proposed to be 1 to 400 parts by mass of an adhesive composition.
  • the adhesive composition is required to have good deformation (elongation recovery rate) from the stretched cured product to the cured product in the state before stretching.
  • the present inventors have now found that there is room for further improvement in the elongation recovery rate of the cured product of the adhesive composition disclosed in Japanese Patent No. 5267571.
  • a cured product obtained by homopolymerizing a 2-cyanoacrylate compound has a storage elastic modulus at 25° C. of greater than 1.0 ⁇ 10 7 Pa and not more than 5.0 ⁇ 10 7 Pa
  • the above Polyfunctional cyanoacrylate compounds include polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, 2-cyanoacrylate compounds of hydrogenated polyisoprene polyols, acrylic polyols, polyurethane polyols, polyvinyl formal , polyvinyl butyral, polyvinyl alcohol, phenolic resin, a silane compound having hydroxyl groups at both ends, and a siloxane compound having hydroxyl groups at both ends.
  • the inventors have found that the cured product obtained from the adhesive composition has an excellent elongation recovery rate compared to the adhesive composition that does not contain the
  • the problem to be solved by the present disclosure is to provide a 2-cyanoacrylate-based adhesive composition that exhibits an excellent elongation recovery rate of the cured product.
  • Means for solving the above problems include the following aspects. ⁇ 1> A cured product obtained by homopolymerizing the 2-cyanoacrylate compound and containing a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound has a storage modulus at 25° C. of 1.0 ⁇ 10 7 Pa or more.
  • the polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic 2-cyanoacrylic acid of a compound selected from the group consisting of polyols, polyurethane polyols, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenolic resins, silane compounds having hydroxyl groups at both ends and siloxane compounds having hydroxyl groups at both ends A 2-cyanoacrylate adhesive composition containing at least one ester.
  • ⁇ 2> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 1 minute passed, the marking The 2-cyanoacrylate adhesive composition according to ⁇ 1> above, wherein the length (L2) between the two is measured, and the elongation recovery rate (%) obtained from the following formula (1) is 55% or more.
  • a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 5 minutes, the mark was taken. 2.
  • Elongation recovery rate (%): ⁇ (L1-L3) / (L1-L0) ⁇ ⁇ 100 (2) (LB-Lb/Lb) ⁇ 100 ⁇ 50% (B) ⁇ 6>
  • a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 30 minutes passed, the marking 2.
  • L 1 each independently represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )-;
  • R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent;
  • R 2 represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent;
  • p represents an integer of 1 to 5; ⁇ 11> Any of the above ⁇ 1> to ⁇ 10>, wherein the cured product obtained by homopolymerizing the 2-cyanoacrylate compound has a maximum loss tangent value (tan ⁇ (max)) of 80°C or less.
  • 2-cyanoacrylate adhesive composition according to any one of the above.
  • the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
  • the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in Synthetic Examples.
  • a combination of two or more preferred aspects is a more preferred aspect.
  • the 2-cyanoacrylate-based adhesive composition of the present disclosure contains a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound, and stores the cured product obtained by homopolymerizing the 2-cyanoacrylate compound at 25°C.
  • the elastic modulus is greater than 1.0 ⁇ 10 7 Pa and 5.0 ⁇ 10 7 Pa or less
  • the polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, The group consisting of polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenolic resin, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends at least one 2-cyanoacrylate ester of a compound selected from
  • the 2 - cyanoacrylate adhesive composition is a 2 - cyanoacrylate compound (
  • a cured product obtained by homopolymerizing a 2-cyanoacrylate compound is also referred to as a homopolymer)
  • polyoxyalkylene polyol polyol
  • polyester polyol polycarbonate polyol
  • polybutadiene polyol hydrogenated polybutadiene polyol
  • polyisoprene polyol hydrogenated poly 2 of compounds selected from the group consisting of isoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenol resin, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends -
  • the 2-cyanoacrylate adhesive composition of the present disclosure has a storage modulus at 25° C. of a cured product obtained by homopolymerization of 2-cyanoacrylate having a storage modulus of more than 1.0 ⁇ 10 7 Pa and not more than 5.0 ⁇ 10 7 Pa.
  • a specific 2-cyanoacrylate compound an acrylate compound (hereinafter also referred to as a specific 2-cyanoacrylate compound).
  • the 2-cyanoacrylate adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds.
  • the storage elastic modulus of the homopolymer at 25° C. is preferably 1.1 ⁇ 10 7 Pa to 4.0 ⁇ 10 7 Pa, more preferably 1.2 ⁇ 10 7 Pa. It is more preferably ⁇ 3.0 ⁇ 10 7 Pa.
  • the storage modulus of a cured product obtained by homopolymerizing a specific 2-cyanoacrylate compound is measured as follows. After injecting the 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, using the dynamic viscoelasticity measuring device, the storage elasticity was measured under the conditions of a frequency of 1 Hz, a temperature of 25 ° C., and a thickness of 300 ⁇ m. measure the rate. After confirming that the storage modulus of the 2-cyanoacrylate compound no longer changes, this is defined as a cured product of the 2-cyanoacrylate compound. Next, using the cured product, the storage elastic modulus of the cured product due to shear is measured in the range of -50 ° C.
  • the temperature at which the cured product obtained by homopolymerizing the specific 2-cyanoacrylate compound shows the maximum loss tangent value is preferably 80° C. or less. It is more preferably 77° C. or lower. Although the lower limit of the temperature is not particularly limited, it can be, for example, 50° C. or higher.
  • the temperature at which the loss tangent of a specific 2-cyanoacrylate compound exhibits a maximum value is measured as follows. After injecting the specific 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, the dynamic viscoelasticity measuring device was used to store the compound under the conditions of a frequency of 1 Hz, a temperature of 25°C, and a thickness of 300 ⁇ m. Measure the elastic modulus. After confirming that the storage modulus of the specific 2-cyanoacrylate compound no longer changes, this is defined as a cured product of the specific 2-cyanoacrylate compound. Using the above cured product, obtain a dynamic viscoelastic spectrum in the range of -50 ° C. to 150 ° C.
  • the dynamic viscoelasticity measuring device that can be used is as described above.
  • the specific 2-cyanoacrylate compound preferably has an ether bond from the viewpoint of the elongation recovery rate of the cured product. Further, from the same viewpoint, the specific 2-cyanoacrylate compound preferably has 2 or more ether bonds, more preferably 2 to 5, even more preferably 2 to 4, and 2 Or it is particularly preferable to have three.
  • the 2-cyanoacrylate adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds having different numbers of ether bonds.
  • the specific 2-cyanoacrylate compound preferably contains a compound represented by the following formula (1).
  • each L 1 independently represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )- , -CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )- is preferable from the viewpoint of the elongation recovery rate of the cured product, and -CH 2 CH 2 - is more preferable.
  • R 1 represents an optionally substituted alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
  • substituents include aryl groups, halogen atoms, alkoxy groups, aryloxy groups, cyano groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, and acyloxy groups.
  • R 1 include a methyl group, an ethyl group, a propyl group, and the like, and from the viewpoint of the elongation recovery rate of the cured product, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.
  • R 2 represents an optionally substituted alkyl group having 1 to 15 carbon atoms, and may be a linear alkyl group or a branched alkyl group.
  • substituents described above for R 1 include the substituents described above for R 1 .
  • R 2 in formula (1) is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having 4 to 13 carbon atoms, from the viewpoint of the elongation recovery rate of the cured product, and more preferably an alkyl group having 4 to 13 carbon atoms. 10 alkyl groups are more preferred.
  • R 2 in formula (1) includes 2-ethylhexyl group, 2-methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylpentyl group and 2-methylheptyl.
  • a 2-ethylhexyl group or an n-butyl group is preferable from the viewpoint of the elongation recovery rate of the product.
  • p represents an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, from the viewpoint of the elongation recovery rate of the cured product, 2 is more preferred.
  • R 2 is a 2-ethylhexyl group, 2 -methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-methylheptyl group, 2-ethylpentyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec -butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-h
  • R 2 is 2-ethylhexyl group, 2-methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylpentyl group, 2-methyl heptyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-
  • the compound represented by formula (1) include 2-(2-ethylhexyloxy)ethyl, 2-(2-butoxyethoxy)ethyl, 2-(1-methylbutoxy)ethyl, 2-(2- Ethylbutoxy)ethyl, 2-(2-methylbutoxy)ethyl, 2-pentyloxyethyl, 2-(2-methylpentyloxy)ethyl, 2-(2-ethylpentyloxy)ethyl, 2-(2-methylhexyl oxy)ethyl, 2-(2-methylheptyloxy)ethyl, 2-hexyloxyethyl, 2-(1-methylpentyloxy)ethyl, 2-heptyloxyethyl, 2-(1-methylhexyloxy)ethyl, 2 -(1-ethylpentyloxy)ethyl, 2-octyloxyethyl, 2-(1-methylheptyloxy)
  • 2-(2-ethylhexyloxy)ethyl-2-cyanoacrylate 2-[2-(2-ethylhexyloxy)ethoxy]ethyl-2-cyanoacrylate or 2 -(2-butoxyethoxy)ethyl-2-cyanoacrylate is preferred, 2-[2-(2-ethylhexyloxy)ethoxy]ethyl-2-cyanoacrylate or 2-(2-butoxyethoxy)ethyl-2-cyanoacrylate 2-cyanoacrylate esters of are more preferred.
  • the content of the specific 2-cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate adhesive composition is preferably 50 parts by mass or more, and is 60 parts by mass or more. more preferably 70 parts by mass or more, particularly preferably 75 parts by mass or more, and most preferably 80 parts by mass or more.
  • the upper limit of the content of the specific 2-cyanoacrylate compound is not particularly limited, but can be, for example, 90 parts by mass or less.
  • the specific 2-cyanoacrylate compound contains the compound represented by formula (1)
  • the specific 2-cyanoacrylate compound contained in the 2-cyanoacrylate-based adhesive composition from the viewpoint of the elongation recovery rate of the cured product.
  • the content of the compound represented by formula (1) with respect to 100 parts by mass is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more, It is particularly preferably 95 parts by mass or more, and may be 100 parts by mass.
  • the 2-cyanoacrylate adhesive composition of the present disclosure includes polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols, acrylic polyols, polyurethane polyols, polyvinyl Formal, polyvinyl butyral, polyvinyl alcohol, phenol resin, at least one 2-cyanoacrylic acid ester of a compound selected from the group consisting of silane compounds having hydroxyl groups at both ends and siloxane compounds having hydroxyl groups at both ends.
  • the polyfunctional cyanoacrylate compound preferably contains a 2-cyanoacrylate ester of a compound selected from the group consisting of polyoxyalkylene polyols and acrylic polyols. More preferably, it contains a 2-cyanoacrylate ester of an oxyalkylene polyol.
  • the polyfunctional cyanoacrylate compound means a compound having two or more cyanoacryloyl groups.
  • the polyoxyalkylene polyol is not particularly limited, but includes polyoxyethylene glycol, polyoxyethylene triol, polyoxyethylene tetraol, polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetraol, polyoxy Tetramethylene glycol, etc., and copolymers with polyols or other glycols, etc. can be used.
  • the polyester polyol is not particularly limited, but general polyester polyol produced by reaction of dibasic acid such as adipic acid with glycol, triol, etc., polycaprolactone polyol obtained by ring-opening polymerization of caprolactone. etc. can be used.
  • the polycarbonate polyol is not particularly limited, but a general polycarbonate diol derived from ethylene carbonate or the like, a copolymer of carbonate and glycol, and the like can be used.
  • Polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and 2-cyanoacrylate of hydrogenated polyisoprene polyol are preferable from the viewpoint of hot water resistance in addition to the flexibility and toughness of the cured product.
  • the polyfunctional cyanoacrylate compound preferably contains a cyanoacrylate ester having 2 to 12 functional groups, and more preferably contains a cyanoacrylate ester having 2 to 6 functional groups. It preferably contains a cyanoacrylate having 2 to 4 functional groups, and particularly preferably contains a cyanoacrylate having 2 or 3 functional groups (bis-cyanoacrylate compound or tris-cyanoacrylate compound). From the viewpoint of the elongation recovery rate of the cured product, the polyfunctional cyanoacrylate compound preferably contains at least one of biscyanoacrylate and triscyanoacrylate.
  • the biscyanoacrylate is preferably a polyoxyalkylene polyol biscyanoacrylate or an alkanediol biscyanoacrylate.
  • the triscyanoacrylate is preferably a polyoxyalkylene polyol tricyanoacrylate.
  • Polyoxyalkylene polyols constituting the polyoxyalkylene polyol biscyanoacrylate compound or polyoxyalkylene polyol tricyanoacrylate include polyoxypropylene glycol (PPG), polyoxyethylene glycol, polyoxytetramethylene glycol, polyoxy Examples include ethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol and the like. Among them, polyoxypropylene glycol (PPG)-biscyanoacrylate or polyoxypropylene glycol (PPG)-triscyanoacrylate is preferable from the viewpoint of elongation recovery rate of the cured product.
  • alkanediol biscyanoacrylates include 1,6-hexanediol-biscyanoacrylate, 1,4-butanediol-biscyanoacrylate, 1,8-octanediol-biscyanoacrylate, 1,9-nonanediol- biscyanoacrylate, 1,10-decanediol-biscyanoacrylate, 1,12-dodecanediol-biscyanoacrylate and the like.
  • the molecular weight or number average molecular weight (Mn) of the polyfunctional cyanoacrylate compound is preferably 1,000 to 50,000, more preferably 1,000 to 10,000. It is more preferably 1,000 to 5,000.
  • Mn is a standard polystyrene conversion value obtained using a gel permeation chromatography (GPC).
  • the content of the polyfunctional cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate compound contained in the 2-cyanoacrylate adhesive composition of the present disclosure is 2 parts by mass to 50 parts by mass. It is preferably 7 parts by mass to 30 parts by mass, more preferably 10 parts by mass to 20 parts by mass, and particularly preferably 13 parts by mass to 18 parts by mass. 14 parts by mass to 17 parts by mass is most preferred.
  • polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, relative to 100 parts by mass of polyfunctional cyanoacrylate contained in the 2-cyanoacrylate adhesive composition The sum of the contents of the 2-cyanoacrylate compounds in the compounds selected from the group consisting of polyisoprene polyols and hydrogenated polyisoprene polyols is preferably 70 parts by mass or more, more preferably 80 parts by mass or more. , more preferably 90 parts by mass or more, particularly preferably 95 parts by mass or more, and may be 100 parts by mass.
  • the 2-cyanoacrylate-based adhesive composition of the present disclosure may contain components other than the specific 2-cyanoacrylate compound and the polyfunctional cyanoacrylate compound within a range that does not impair its properties.
  • Other components include 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds, stabilizers, curing accelerators, plasticizers, thickeners, particles, colorants, fragrances, solvents, strength improvers, and the like. .
  • 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds include methyl, ethyl, chloroethyl, n-propyl, i-propyl, allyl, propargyl, n-butyl, i-butyl, n- Pentyl, n-hexyl, cyclohexyl, phenyl, tetrahydrofurfuryl, heptyl, 2-ethylhexyl, n-octyl, 2-octyl, n-nonyl, oxononyl, n-decyl, n-dodecyl, methoxyethyl, methoxypropyl, methoxyisopropyl , methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxyisopropyl, propoxymethyl, propoxyethyl, isopropoxyethyl,
  • Stabilizers include (1) aliphatic sulfonic acids such as sulfur dioxide and methanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, and trifluorides such as boron trifluoride methanol and boron trifluoride diethyl ether.
  • examples include boron complexes, anionic polymerization inhibitors such as HBF 4 and trialkylborate, and radical polymerization inhibitors such as (2) hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, catechol and pyrogallol. These stabilizers may be used alone or in combination of two or more.
  • Curing accelerators include polyether compounds, calixarenes, thiacalixarenes, pyrogallolarenes, onium salts and the like. One of these curing accelerators may be used alone, or two or more thereof may be used in combination.
  • Plasticizers include acetyl triethyl citrate, acetyl tributyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, and 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, caproic acid triglyceride, 2-ethylhexyl benzoate, dipropylene glycol dibenzoate and the like.
  • acetyl tributyl citrate, dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate or dipropylene glycol dipropylene glycol are preferred because of their good compatibility with 2-cyanoacrylate compounds and high plasticization efficiency. Benzoates are preferred. These plasticizers may be used alone or in combination of two or more.
  • thickeners examples include polymethyl methacrylate, copolymers of methyl methacrylate and acrylic acid esters, copolymers of methyl methacrylate and other methacrylic acid esters, acrylic rubber, polyvinyl acetate, polyvinyl chloride, Polyurethane resins, polyamide resins, polystyrene, cellulose esters, polyalkyl-2-cyanoacrylic acid esters, ethylene-vinyl acetate copolymers, and the like. These thickeners may be used alone or in combination of two or more.
  • the 2-cyanoacrylate-based adhesive composition of the present disclosure may contain particles to the extent that the properties thereof are not impaired, and are thus formed by using the 2-cyanoacrylate-based adhesive composition.
  • the thickness of the adhesive layer can be adjusted.
  • the average particle diameter of the particles is preferably 10 ⁇ m to 200 ⁇ m, more preferably 15 ⁇ m to 200 ⁇ m, even 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 or the like used and does not cause deterioration such as polymerization.
  • Particles include thermoplastic resins such as polyethylene, polypropylene, polymethylpentene, acrylic resins, polyvinyl chloride, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polysulfone, and polyphenylene oxide; unsaturated polyesters, divinylbenzene polymers, Crosslinked resins such as divinylbenzene-styrene copolymers, divinylbenzene-(meth)acrylate copolymers, and diallyl phthalate polymers; inorganic compounds such as spherical silica, glass beads, and glass fibers; silicone compounds; Examples include organic-inorganic composite particles containing a polysiloxane skeleton.
  • thermoplastic resins such as polyethylene, polypropylene, polymethylpentene, acrylic resins, polyvinyl chloride, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polysulf
  • the content of the particles is not particularly limited, but from the viewpoint of curing speed, adhesive strength, etc., the amount of particles per 100 mass of the 2-cyanoacrylate compound contained in the 2-cyanoacrylate adhesive composition of the present disclosure.
  • the content is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, even more preferably 1 to 3 parts by mass.
  • the average particle diameter of particles is a volume-based average value measured by a laser diffraction particle size distribution analyzer.
  • a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after one minute has passed
  • the length (L2) is measured, and the elongation recovery rate (%) obtained from the following formula (1) is preferably 55% or more, more preferably 58% or more, and 60% or more.
  • the elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity. Elongation recovery rate (%): ⁇ (L1-L2) / (L1-L0) ⁇ ⁇ 100 (1)
  • a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after 5 minutes
  • the length (L3) is measured, and the elongation recovery rate (%) obtained from the following formula (2) is preferably 65% or more, more preferably 67% or more, and 70% or more. is more preferable, and 75% or more is particularly preferable.
  • the elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity. Elongation recovery rate (%): ⁇ (L1-L3) / (L1-L0) ⁇ ⁇ 100 (2)
  • a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after 30 minutes
  • the length (L4) is measured, and the elongation recovery rate (%) obtained from the following formula (3) is preferably 70% or more, more preferably 73% or more, and 75% or more. is more preferable, and 80% or more is particularly preferable.
  • the elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity. Elongation recovery rate (%): ⁇ (L1-L4) / (L1-L0) ⁇ ⁇ 100 (3)
  • a Strograph V20-C manufactured by Toyo Seiki Seisakusho Co., Ltd. or a similar device can be used.
  • the cured product used for the measurement of the elongation recovery rate is produced as follows. First, a silicone rubber mold with a thickness of 1 mm is placed on a release polyethylene terephthalate (PET) film. Next, 1 ⁇ L of triethanolamine is added to 1 g of the 2-cyanoacrylate-based adhesive composition of the present disclosure, stirred, and poured into the mold.
  • the mold and the adhesive composition were covered with the separately prepared release PET film, sandwiched between glass plates, and then at a temperature of 25 ° C. and a relative humidity of 50%. Allow 24 hours to fully cure. After curing, the mold and release PET film are removed to obtain a cured product with a width of 5 mm, a length of 50 mm and a thickness of 1 mm.
  • the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition of the present disclosure obtained from the above formula (1) is LA
  • La is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LA was measured
  • the following formula (A) is preferably satisfied. (LA ⁇ La/La) ⁇ 100 ⁇ 50% (A)
  • LB is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition of the present disclosure obtained from the above formula (2)
  • the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LB was measured is Lb
  • the following formula (B) is preferably satisfied. (LB-Lb/Lb) ⁇ 100 ⁇ 50% (B)
  • the 2-cyanoacrylate adhesive composition of the present disclosure can be used in various applications such as construction applications, automobile-related applications, and electrical/electronic material applications.
  • Architectural applications include elastic adhesives for construction, adhesives for double glazing, adhesives for artificial marble, and the like.
  • Examples of electrical/electronic material applications include resins for encapsulating semiconductors, insulating materials for printed wiring boards, insulating coating materials for electric wires and cables, electronic component coating agents, electronic component potting agents, electrical component sealers, and the like.
  • the 2-cyanoacrylate adhesive composition of the present disclosure can also be used for packings, O-rings and the like.
  • waterproof packings Specifically, waterproof packings, insect-proof packings, anti-vibration/sound absorption and air seal materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater packings, electrode packings, safety valve diaphragms, solenoid valves, Waterproof packing for steam oven ranges and jar rice cookers, water tank packing, water absorption valves, water receiving packing, heat insulation heater packing, oil packing for combustion equipment such as steam outlet seals, O-rings, drain packing, feed/intake packing, Anti-vibration rubber, oil fill port packing, oil gauge packing, diaphragm valve, etc., speaker gasket for audio equipment, speaker edge, etc.
  • the adhesive composition of the present invention can be used in a gasket method [MIPG (Mold In Place Gasket), FIPG (Mold In Place Gasket), FIPG ( Formed In Place Gasket), CIPG (Cured In Place Gasket)].
  • 2-cyanoacrylate-based adhesive composition of the present disclosure can be suitably used for resins or metals as adherends, and can be more suitably used for rubber.
  • the storage elastic modulus at 25°C was determined.
  • the storage elastic modulus at 25° C. of the cured product obtained by homopolymerizing the 2-cyanoacrylate compound used in each example and each comparative example is shown. summarized in 1.
  • Example 1 To 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 is blended so as to have the content described in Table 1, stirred until uniform, and the 2-cyanoacrylate A system adhesive composition was prepared.
  • PPG4000TCA was synthesized by the following method.
  • a 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene.
  • the reaction system was heated to 60° C., and while blowing nitrogen gas from a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; Polyether G-4000"] dissolved in 16 mL of benzene was added. The temperature was then maintained at 60° C. and stirred for 30 minutes.
  • PPG3000BCA was synthesized by the following method.
  • a 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. Thereafter, the reaction system was heated to 60° C., and while blowing nitrogen gas through a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; ADEKA POLYOL P-3000"] dissolved in 18 mL of benzene was added. The temperature was then maintained at 60° C. and stirred for 30 minutes.
  • PPG10000BCA was synthesized by the following method.
  • a 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. Thereafter, the temperature of the reaction system is raised to 60° C., and while nitrogen gas is blown from a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; A solution of 94.5 g of Preminol S-4011"] dissolved in 60 mL of benzene was added. The temperature was then maintained at 60° C. and stirred for 30 minutes.
  • elongation recovery rates of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig were 90%, 94%, and 90%, respectively.
  • 2-cyanoacrylate adhesive composition produced in Example 3 in the same manner as in Example 1, elongation recovery rates of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig were 90%, 91% and 85%, respectively.
  • the 2-cyanoacrylate adhesive compositions produced in Examples are excellent in the rate of increase in elongation recovery rate of the cured product.
  • the recovery of elongation of the cured product has progressed greatly 5 minutes after the fixation of the jig was released.
  • the rate of increase in the elongation recovery rate at 30 minutes after the release was smaller than the rate of increase in elongation recovery rate at the time of 5 minutes.
  • Table 1 summarizes the rate of increase in the elongation recovery rate of each example and comparative example. Comparative Examples 1 to 4 and Comparative Example 8, which serve as the reference for the rate of increase in elongation recovery rate, are all listed as "1" in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition d'adhésif à base de 2-cyanoacrylate qui comprend un composé 2-cyanoacrylate, et un composé cyanoacrylate polyfonctionnel. Le module d'élasticité de conservation à 25°C d'un objet durci constitué par homopolymérisation dudit composé 2-cyanoacrylate, est supérieur à １,０×１０７Ｐａ et inférieur ou égal à ５,０×１０７Ｐａ. Ledit composé cyanoacrylate polyfonctionnel contient au moins une sorte de composé 2-cyanoacrylate d'un composé choisi dans un groupe constitué d'un polyoxyalkylène polyol, ou similaire.
PCT/JP2022/027096 2021-07-12 2022-07-08 Composition d'adhésif à base de 2-cyanoacrylate WO2023286709A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008056516A1 (fr) * 2006-11-07 2008-05-15 Terumo Kabushiki Kaisha Adhésif à base de 2-cyanoacrylate destiné à des organismes vivants
WO2010074095A1 (fr) * 2008-12-25 2010-07-01 東亞合成株式会社 Composition adhésive
US20170260422A1 (en) * 2014-09-12 2017-09-14 Afinitica Technologies, S. L. Fast and elastic adhesive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008056516A1 (fr) * 2006-11-07 2008-05-15 Terumo Kabushiki Kaisha Adhésif à base de 2-cyanoacrylate destiné à des organismes vivants
WO2010074095A1 (fr) * 2008-12-25 2010-07-01 東亞合成株式会社 Composition adhésive
US20170260422A1 (en) * 2014-09-12 2017-09-14 Afinitica Technologies, S. L. Fast and elastic adhesive

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