WO2020085334A1 - Composition d'adhésif photodurcissable - Google Patents

Composition d'adhésif photodurcissable Download PDF

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Publication number
WO2020085334A1
WO2020085334A1 PCT/JP2019/041399 JP2019041399W WO2020085334A1 WO 2020085334 A1 WO2020085334 A1 WO 2020085334A1 JP 2019041399 W JP2019041399 W JP 2019041399W WO 2020085334 A1 WO2020085334 A1 WO 2020085334A1
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Prior art keywords
compound
group
adhesive composition
photocurable adhesive
polymerization inhibitor
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PCT/JP2019/041399
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English (en)
Japanese (ja)
Inventor
謙一 石▲崎▼
健人 大村
絵利香 一色
洋慈 堀江
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to JP2020553408A priority Critical patent/JP7548012B2/ja
Publication of WO2020085334A1 publication Critical patent/WO2020085334A1/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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Definitions

  • the present invention relates to a photocurable adhesive composition.
  • An adhesive composition containing a 2-cyanoacrylate compound rapidly initiates polymerization due to a small amount of water existing near the surface of the adherend, and almost all of the adherends made of various materials can be used for several seconds to several minutes. Since it adheres in an extremely short time and has a strong adhesive force, it is used as a main component of an instant adhesive in a wide range of fields such as electric, electronic, mechanical parts, precision machinery, household products and medical care.
  • Patent Document 1 discloses a photo-curing method comprising a transition metal metallocene compound of Group VIII of the Periodic Table containing (A) ⁇ -cyanoacrylate (B) aromatic electron ligand as an essential component. A sex composition is described.
  • Patent Document 2 discloses a photocurable composition comprising (A) ⁇ -cyanoacrylate, (B) lower alkyl-substituted ferrocene compound, and (C) photocuring accelerator as essential components. Have been described.
  • Patent Document 3 (A) ⁇ -cyanoacrylate, (B) a transition metal metallocene compound of Group VIII of the periodic table having an aromatic electron ligand, and (C) the following general formula A photocurable composition comprising a photocuring accelerator having a structure shown in (1) is described.
  • R is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen group, or an alkylthio group having 1 to 8 carbon atoms, and each R may be the same or different.
  • Patent Document 4 (A) ⁇ -cyanoacrylate, (B) (meth) polyfunctional compound having an acryloyl group, (C) peroxide, (D) aromatic electron-based coordination as essential components.
  • a cyanoacrylate-based adhesive composition which contains a child-containing periodic group 8 transition metal metallocene compound and (E) an intramolecularly cleaved photoradical initiator and can be moisture-cured and photocured is described.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 9-249708 Patent Document 2: Japanese Patent Application Laid-Open No. 11-166006 Patent Document 3: Japanese Patent Application Laid-Open No. 2003-277422 Patent Document 4: Japanese Patent Application Laid-Open No. 2007-217484
  • the problem to be solved by the present invention is to provide a photocurable adhesive composition having excellent storage stability.
  • Means for solving the above problems include the following aspects.
  • a Group 8 transition metal metallocene compound and a 2-cyanoacrylate compound are contained and a compound having a benzoquinone structure is not contained, or the content of the compound having a benzoquinone structure is more than 0 ppm and less than 4 ppm.
  • Photocurable adhesive composition ⁇ 2> The photocurable adhesive composition according to ⁇ 1>, wherein the Group 8 transition metal metallocene compound is at least one compound selected from the group consisting of ferrocene and ruthenocene.
  • ⁇ 3> The photocurable adhesive composition according to ⁇ 1> or ⁇ 2>, wherein the Group 8 transition metal metallocene compound is ferrocene.
  • ⁇ 4> The photocurable adhesive composition according to any one of ⁇ 1> to ⁇ 3>, which further contains a photoradical generator.
  • ⁇ 5> The photocurable adhesive composition according to ⁇ 4>, wherein the photoradical generator is at least one compound selected from the group consisting of an acylgermane compound, an acylphosphine oxide compound and an alkylphenone compound.
  • ⁇ 6> The photocurable adhesive composition according to any one of ⁇ 1> to ⁇ 5>, which further contains a polymerization inhibitor.
  • ⁇ 7> The photocurable adhesive composition according to ⁇ 6>, wherein the polymerization inhibitor contains a phenolic radical polymerization inhibitor.
  • a photocurable adhesive composition having excellent storage stability can be provided.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • the term “step” is included in this term as long as the intended purpose of the step is achieved, not only when it is an independent step but also when it cannot be clearly distinguished from other steps.
  • “mass%” and “weight%” have the same meaning
  • “mass part” and “weight part” have the same meaning.
  • a combination of two or more preferable aspects is a more preferable aspect.
  • (meth) acryloyl represents both acryloyl and methacryloyl, or either
  • (meth) acryloxy represents both acryloxy and methacryloxy.
  • the hydrocarbon chain may be described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted.
  • C carbon
  • H hydrogen
  • the photocurable adhesive composition of the present invention contains a Group 8 transition metal metallocene compound and a 2-cyanoacrylate compound, and does not contain a compound having a benzoquinone structure or contains a compound having a benzoquinone structure.
  • the amount is more than 0 ppm and less than 4 ppm.
  • a compound having a hydroquinone structure such as hydroquinone is often used as a polymerization inhibitor at the time of depolymerization.
  • a compound having a hydroquinone structure is used in the production of a 2-cyanoacrylate compound, the compound having a hydroquinone structure is oxidized due to the action of impurities or decomposed products, and a compound having a benzoquinone structure is produced in a trace amount, and distillation, etc.
  • the compound having a benzoquinone structure in the 2-cyanoacrylate compound cannot be completely removed even by carrying out, and that the presence of the compound having a benzoquinone structure greatly contributes to the storage stability of the photocurable adhesive composition.
  • the present inventors have found out. As a result of intensive studies by the present inventors, the 2-cyanoacrylate-based photocurable adhesive composition contains no compound having a benzoquinone structure, or the content of the compound having a benzoquinone structure is more than 0 ppm and less than 4 ppm. It was found that a photocurable adhesive composition having excellent storage stability can be provided by using such a composition.
  • the photocurable adhesive composition of the present invention does not contain a compound having a benzoquinone structure, or the content of the compound having a benzoquinone structure is more than 0 ppm and less than 4 ppm. Further, the photocurable adhesive composition of the present invention does not contain a compound having a benzoquinone structure, or the content of the compound having a benzoquinone structure is more than 0 ppm and 3 ppm or less from the viewpoint of storage stability.
  • the compound having a benzoquinone structure is not contained, or the content of the compound having a benzoquinone structure is more preferably more than 0 ppm and 2 ppm or less, and the compound having a benzoquinone structure is not contained, or the benzoquinone structure is contained. It is more preferable that the content of the compound having is more than 0 ppm and not more than 1.5 ppm.
  • the photocurable adhesive composition of this invention contains the compound which has 2 or more types of benzoquinone structures, the said content is the total content of the compound which has 2 or more types of benzoquinone structures.
  • the compound having a benzoquinone structure in the present invention may be a compound having a 1,4-benzoquinone structure or a compound having a 1,2-benzoquinone structure.
  • Examples of the compound having a benzoquinone structure include 1,4-benzoquinone, 1,2-benzoquinone, 1,4-naphthoquinone, 1,2-naphthoquinone, and 9,10-anthraquinone.
  • the method for reducing the content of the compound having a benzoquinone structure in the photocurable adhesive composition of the present invention is not particularly limited, but the 2-cyanoacrylate compound used does not contain a compound having a benzoquinone structure, Alternatively, a method of using a 2-cyanoacrylate compound having a small content is preferable.
  • Examples of the method for producing a 2-cyanoacrylate compound include depolymerizing a 2-cyanoacrylate polycondensate which is a condensate of a cyanoacetic acid ester compound and a formaldehyde compound, and distilling the obtained crude 2-cyanoacrylate compound. Then, a method for obtaining a purified 2-cyanoacrylate compound is known.
  • a specific example of a method for reducing the content of the compound having a benzoquinone structure in the 2-cyanoacrylate compound is, for example, a method of using a polymerization inhibitor having no hydroquinone structure at the time of depolymerization.
  • a more preferable method is to use a polymerization inhibitor having no hydroquinone structure at the time and during the distillation.
  • the polymerization inhibitor having no hydroquinone structure preferably contains a compound having a phenolic hydroxy group, more preferably a compound represented by the following formula (1), and the following formula:
  • the compound represented by (2) is particularly preferable.
  • R 1 to R 5 are each independently a hydrogen atom or a hydroxy group (excluding a phenolic hydroxy group), which is bonded to each other to form a ring.
  • R 6 represents a hydrogen atom or an alkyl group
  • R 7 to R 10 each independently represents an alkyl group, a cycloalkyl group or an alkenyl group
  • R 11 represents a hydrogen atom
  • R 1 to R 5 is preferably the above-mentioned substituent, and R 1 and R 5 are more preferably at least the above-mentioned substituents, R 1 It is particularly preferable that 1 , R 3 and R 5 are at least the above substituents.
  • R 1 and R 5 in formula (1) are each independently a linear or branched alkyl group, a cycloalkyl group, an alkyl group having a structure having a phenolic hydroxy group, or (meth) from the viewpoint of storage stability.
  • R 1 is a linear or branched alkyl group
  • R 5 is an alkyl group having a structure having a phenolic hydroxy group, or (meth) acryloxyphenyl It is more preferably an alkyl group having a structure
  • R 1 is a linear or branched alkyl group
  • R 5 is particularly preferably an alkyl group having a (meth) acryloxyphenyl structure.
  • R 3 in the formula (1) is preferably a hydrogen atom, an alkyl group or an alkoxy group, and is a linear or branched alkyl group, a cycloalkyl group or an alkoxy group.
  • the alkyl group for R 1 , R 3 and R 5 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • a linear or branched alkyl group, a cycloalkyl group having 1 to 6 carbon atoms, a t-butyl group, or a 2-methyl-2-butyl group is more preferable, and a methyl group, a t-butyl group, or 2 It is particularly preferably a methyl-2-butyl group.
  • the alkyl group may be linear, may have a branch, may have a ring structure, and may have a substituent.
  • the substituent may be a group that does not lose its ability to inhibit polymerization, and examples thereof include a halogen atom, an alkoxy group, and an aryl group. Further, the substituent may be further substituted with at least one kind of group selected from the group consisting of the substituent and an alkyl group.
  • R 2 and R 4 are each independently preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • R 6 in formula (2) is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 7 and R 10 in the formula (2) are preferably a tertiary alkyl group, more preferably a C 4-8 tertiary alkyl group, and t- A butyl group or a 2-methyl-2-butyl group is particularly preferable.
  • R 8 and R 9 in the formula (2) are preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group, such as a methyl group, a t-butyl group, and 2-methyl-2-.
  • R 11 in formula (2) is preferably a hydrogen atom or a (meth) acryloyl group.
  • the 5% weight loss temperature of the polymerization inhibitor having no hydroquinone structure in a nitrogen atmosphere is -150 ° C to the boiling point of the 2-cyanoacrylate compound contained in the photocurable adhesive composition of the present invention. It is preferable to include a compound in the range of + 50 ° C.
  • the polymerization inhibitors having no hydroquinone structure are 2,2′-methylenebis (6-tert-butyl-p-cresol) (221 ° C.) and 2,2′-methylenebis (4 -Ethyl-6-tert-butyl-phenol) (229 ° C), 2,2'-methylenebis (4-methyl-6-tert-butylphenol) monoacrylate (234 ° C), 2,2'-ethylenebis (4,4) At least one selected from the group consisting of 6-di-tert-amylphenol) monoacrylate (253 ° C.) and 2,2′-methylenebis (6- (1-methylcyclohexyl) -p-cresol) (285 ° C.) It is preferable that the compound is The temperatures in parentheses are all 5% weight loss temperatures.
  • the polymerization inhibitor having no hydroquinone structure may be removed from the 2-cyanoacrylate compound used in the depolymerization and the distillation, or may not be completely removed from the 2-cyanoacrylate compound. It may be contained in the photo-curable adhesive composition.
  • the photocurable adhesive composition of the present invention contains a Group 8 transition metal metallocene compound. It is estimated that the Group 8 transition metal metallocene compound functions as a photopolymerization initiator. Further, since the light absorption wavelength of the Group 8 transition metal metallocene compound is also on the long wavelength side of 500 nm or more, the photocurable adhesive composition of the present invention has a wider wavelength range, that is, an ultraviolet range and a visible range. Light curing is possible even with light in the light range.
  • Group 8 transition metal metallocene compound examples include a ferrocene compound in which the transition metal is iron, an osmocene compound in which osmium is a ruthenocene compound in which ruthenium is a cobaltocene compound in which cobalt is a nickelocene compound. Mention may be made of metallocene compounds having a Group 8 transition metal element in the table. Among these, at least one compound selected from the group consisting of ferrocene compounds and ruthenocene compounds is preferable from the viewpoint of photocurability and storage stability.
  • Group 8 transition metal metallocene compound examples include, for example, ferrocene, ethylferrocene, n-butylferrocene, benzoylferrocene, acetylferrocene, t-amylferrocene, 1,1′-dimethylferrocene, 1,1 ′.
  • -Di-n-butylferrocene 1,1'-dibenzoylferrocene, 1,1'-di (acetylcyclopentadienyl) iron, bis (pentamethylcyclopentadienyl) iron, bis (cyclopentadienyl) Examples thereof include osmium, bis (pentamethylcyclopentadienyl) osmium, ruthenocene (bis (cyclopentadienyl) ruthenium), and bis (pentamethylcyclopentadienyl) ruthenium.
  • the Group 8 transition metal metallocene compound a transition metal metallocene compound of Group 8 of the periodic table having an aromatic electron type ligand described in JP-A-2003-277422 can be preferably used.
  • the Group 8 transition metal metallocene compound is a group consisting of ferrocene, ethylferrocene, n-butylferrocene, benzoylferrocene and ruthenocene, from the viewpoint of photocurability, adhesion rate, cost-effectiveness and storage stability. It is preferable that it is at least one compound selected from among, and it is particularly preferable that it is at least one compound selected from the group consisting of ferrocene, benzoylferrocene and ruthenocene.
  • the photocurable adhesive composition of the present invention may contain one kind of Group 8 transition metal metallocene compound alone, or may contain two or more kinds thereof.
  • the content of the Group 8 transition metal metallocene compound in the photocurable adhesive composition of the present invention is preferably 1 ppm to 50,000 ppm, and preferably 10 ppm to 10 ppm, from the viewpoint of photocurability and storage stability. It is more preferably 2,000 ppm, particularly preferably 20 ppm to 2,000 ppm.
  • the photocurable adhesive composition of the present invention contains a 2-cyanoacrylate compound.
  • the 2-cyanoacrylate compound used in the present invention is not particularly limited, but a compound represented by the following formula (C) is preferable.
  • R is a saturated or unsaturated, straight-chain hydrocarbon group, branched chain hydrocarbon group or cyclic hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom, or Represents an aromatic hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom.
  • R contains an ether bond
  • either or both of the ether-bonded hydrocarbon residual chains may be a saturated or unsaturated C5 to C20 straight chain which may have a halogen atom. It is a chain hydrocarbon group, a branched chain hydrocarbon group or a cyclic hydrocarbon group, or an aromatic group having 5 to 20 carbon atoms which may have a halogen atom.
  • 2-cyanoacrylate compound examples include methyl, ethyl, chloroethyl, n-propyl, i-propyl, allyl, propargyl, n-butyl, i-butyl, n-pentyl and n- of 2-cyanoacrylic acid.
  • 2-cyanoacrylate compounds include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, cyclohexyl, phenyl, tetrahydrofurfuryl, 2-ethylhexyl of 2-cyanoacrylic acid, Preferable examples include n-octyl, 2-octyl, 2-methoxyethyl, 2-ethoxyethyl ester, and 1- (2-methoxy-1-methylethoxy) propyl.
  • the photocurable adhesive composition of the present invention may include one type of the 2-cyanoacrylate compound alone or may include two or more types.
  • the content of the 2-cyanoacrylate compound in the photocurable adhesive composition of the present invention is preferably 40% by mass or more, and more preferably 60% by mass or more, from the viewpoint of curability, adhesion speed, and adhesive strength. More preferably.
  • the photocurable adhesive composition of the present invention preferably further contains a photoradical generator.
  • a photo-radical generator a known photo-radical generator used when photopolymerizing a radical-polymerizable compound can be used.
  • the photoradical generator include an acylgermane-based compound, an acylphosphine oxide-based compound, a hydroxy group, an acetophenone-based compound that does not have a nitrogen atom and a thioether bond, and a benzoin-based compound that does not have a hydroxy group, a nitrogen atom, and a thioether bond.
  • an acylgermane compound is preferable from the viewpoint of photocurability, adhesion speed, and storage stability.
  • the acylgermane compound is preferably a monoacylgermane compound or a bisacylgermane compound, more preferably a bisacylgermane compound.
  • Preferable examples of the acylgermane compound include Ivocerin (manufactured by Ivoclar Vivadent).
  • acylphosphine oxide-based compound monoacylphosphine oxide-based compounds and bisacylphosphine oxide-based compounds are preferable, and bisacylphosphine oxide-based compounds are more preferable.
  • Preferred examples of the monoacylphosphine oxide compound include compounds represented by the following formula (A-1).
  • R A1 and R A2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, or 1 to 3 carbon atoms having 1 to 3 carbon atoms. Represents an phenyl group substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms, and R A3 is a linear or branched alkyl group having 1 to 18 carbon atoms, which is unsubstituted or substituted with an acetyloxy group.
  • a cycloalkyl group having 3 to 12 carbon atoms an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group which is unsubstituted or substituted by a halogen atom; or by the following formula (A-2) Represents a group represented.
  • R A4 and R A5 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, or 1 to 3 carbon atoms having 1 to 3 carbon atoms.
  • 8 represents a phenyl group substituted by an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms
  • X A1 represents a p-phenylene group.
  • acylphosphine oxide compounds include methylisobutyroylmethylphosphinate, methylisobutyroylphenylphosphinate, methylpivaloylphosphinate, methyl-2-ethylhexanoylphosphinate, and isopropyl-2-ethylhexanoylphenylphosphonate.
  • Preferred examples of the bisphosphine oxide-based compound include compounds represented by the following formula (A-3).
  • R p in the formula (A-3) is unsubstituted, is an alkyl group having 1 to 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, or a halogen atom, and each R p is the same. It may be different.
  • the alkyl group having 1 to 12 carbon atoms in R p in formula (A-3) may be linear or branched, and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. , Tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl groups. It is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the alkylthio group having 1 to 8 carbon atoms in R p in formula (A-3) may be linear or branched, and examples thereof include methylthio, ethylthio, propylthio, isopropylthio, butylthio, tert-butylthio, Hexylthio or octylthio are mentioned. Of these, methylthio is preferable.
  • the halogen atom include chlorine atom, bromine atom, and iodine atom. Of these, chlorine atom is preferable.
  • bisacylphosphine oxide compound examples include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.
  • acetophenone compound examples include 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone and diethoxyacetophenone.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl methyl ketal.
  • the photoradical generators are dibenzoyldiethylgermanium, bis (4-methoxybenzoyl) dimethylgermanium, and bis (4-methoxybenzoyl) diethylgermanium from the viewpoints of photocurability, adhesion rate, and storage stability.
  • dibenzoyldiethylgermanium bis (4-methoxybenzoyl) dimethylgermanium, bis (4-methoxybenzoyl) diethylgermanium, bis (4-methylbenzoyl) diethylgermane Maniumu, more preferably bis (4-methylbenzoyl) at least one compound selected from the group consisting of dimethyl germanium and dibenzo dichloride butyl germanium.
  • the photocurable adhesive composition of the present invention may contain one type of photoradical generator alone, or may contain two or more types.
  • the content of the photoradical generator in the photocurable adhesive composition of the present invention is 0 with respect to the total mass of the photocurable adhesive composition from the viewpoint of photocurability, adhesion speed, and storage stability.
  • the amount is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 2% by mass, and particularly preferably 0.05% by mass to 1% by mass.
  • the photocurable adhesive composition of the present invention preferably further contains a polymerization inhibitor from the viewpoint of storage stability.
  • a polymerization inhibitor a known polymerization inhibitor can be used.
  • Preferred examples of the polymerization inhibitor include diphosphorus pentoxide, SO 2 , p-toluene sulfonic acid, methane sulfonic acid, propane sultone, BF 3 complex and other anionic polymerization inhibitors having no hydroquinone structure.
  • a phenolic radical polymerization inhibitor is preferably used from the viewpoint of storage stability.
  • the phenol-based radical polymerization inhibitor include radical polymerization inhibitors having no hydroquinone structure, such as the compounds represented by the formula (1) or the formula (2).
  • radical polymerization inhibitor having no hydroquinone structure from the viewpoint of storage stability, mequinol, butylhydroxyanisole, dibutylhydroxytoluene, di-tert-butylhydroxytoluene, 6-tert-butyl-4-xylenol, 2,6 -Di-tert-butylphenol, 2,2'-methylenebis (6-tert-butyl-p-cresol), 2,2'-methylenebis (4-ethyl-6-tert-butyl-phenol), 2,2'- Methylenebis (4-methyl-6-tert-butylphenol) monoacrylate, 2,2'-ethylenebis (4,6-di-tert-amylphenol) monoacrylate and 2,2'-methylenebis (6- (1-methyl A cyclohexyl) -p-cresol)
  • the phenolic radical polymerization inhibitor preferably contains a radical polymerization inhibitor having a hydroquinone structure, and more preferably contains a radical polymerization inhibitor having a 1,4-hydroquinone structure.
  • the radical polymerization inhibitor having a hydroquinone structure is 1,4-hydroquinone, 1,2-hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, 2,6-di-tert-butylhydroquinone from the viewpoint of storage stability.
  • At least one compound selected from the group consisting of 1,4-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, and 9,10-dihydroxyanthracene is preferable, and 1,4-hydroquinone, 1,2-hydroquinone, More preferably, it is at least one selected from the group consisting of methylhydroquinone, methoxyhydroquinone, 2,6-dimethylhydroquinone and 2,6-di-tert-butylhydroquinone, and hydroquinone, methylhydroquinone and methoxyha are preferred. It is particularly preferred from the group consisting of Dorokinon is at least one selected.
  • the radical polymerization inhibitor having a hydroquinone structure is preferably added after the distillation and purification at the time of preparing the photocurable adhesive composition or at the time of producing the 2-cyanoacrylate compound as a raw material. It is more preferable to prepare the curable adhesive composition.
  • the photocurable adhesive composition of the present invention may contain one type of polymerization inhibitor or two or more types of polymerization inhibitors. Among them, from the viewpoint of storage stability, it is preferable to contain an anionic polymerization inhibitor having no hydroquinone structure, and it is more preferable to contain a radical polymerization inhibitor having no hydroquinone structure and an anionic polymerization inhibitor having no hydroquinone structure. It is particularly preferable to contain a radical polymerization inhibitor having a hydroquinone structure, a radical polymerization inhibitor having no hydroquinone structure, and an anionic polymerization inhibitor having no hydroquinone structure.
  • the content of the polymerization inhibitor is preferably 50 ppm to 1% by mass, and more preferably 20 ppm to 5,000 ppm, based on the total mass of the photocurable adhesive composition. Further, the content of the radical polymerization inhibitor having a hydroquinone structure is preferably 10 ppm or more and 1000 ppm or less, and more preferably 20 ppm or more and 500 ppm or less.
  • the photocurable adhesive composition of the present invention may contain an additive other than the above-mentioned components.
  • Other additives are not particularly limited, and known additives can be used.
  • As other additives for example, anionic polymerization accelerators, plasticizers, thickeners, fumed silica, particles, fillers, colorants, fragrances, solvents, strength improvers, etc., depending on the purpose, etc.
  • An appropriate amount of the adhesive composition can be blended within a range that does not impair the curability and the adhesive strength of the adhesive composition.
  • the content of other additives is not particularly limited, but is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total mass of the photocurable adhesive composition.
  • anionic polymerization accelerators include polyalkylene oxides, crown ethers, silacrown ethers, calixarenes, cyclodextrins, and pyrogallol cyclic compounds.
  • the polyalkylene oxides are polyalkylene oxides and derivatives thereof, and include, for example, JP-B-60-37836, JP-B-1-43790, JP-A-63-128088, and JP-A-3-167279. Examples thereof include those disclosed in the gazette, US Pat. No. 4,386,193, US Pat. No. 4,424,327 and the like.
  • polyalkylene oxide such as diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol
  • polyethylene glycol monoalkyl ester such as diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol
  • polyethylene glycol dialkyl ester such as polyethylene glycol dialkyl ester
  • polypropylene glycol dialkyl ester diethylene glycol monoalkyl ether
  • diethylene glycol examples include polyalkylene oxide derivatives such as dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.
  • the crown ethers include those disclosed in Japanese Examined Patent Publication No. 55-2236 and Japanese Patent Laid-Open No. 3-167279.
  • silacrown ethers include those disclosed in JP-A-60-168775. Specific examples thereof include dimethylsila-11-crown-4, dimethylsila-14-crown-5, dimethylsila-17-crown-6 and the like.
  • calixarene examples include those disclosed in JP-A-60-179482, JP-A-62-235379, JP-A-63-88152 and the like.
  • Examples of cyclodextrins include those disclosed in JP-A-5-505835. Specific examples include ⁇ -, ⁇ -, or ⁇ -cyclodextrin.
  • Examples of the pyrogallol cyclic compounds include compounds disclosed in JP 2000-191600 A and the like. Specifically, 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 can be mentioned. These anionic polymerization accelerators may be used alone or in combination of two or more.
  • the plasticizer can be contained within a range that does not impair the effects of the present invention.
  • the plasticizer include triethyl acetyl citrate, tributyl acetyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, and phthalic acid.
  • tributyl acetyl citrate, dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate, and dipropylene glycol are well compatible with 2-cyanoacrylic acid ester and have high plasticization efficiency.
  • Dibenzoate is preferred.
  • These plasticizers may be used alone or in combination of two or more.
  • the content of the plasticizer is not particularly limited, but when the content of the 2-cyanoacrylate compound is 100 parts by mass, preferably 3 parts by mass to 50 parts by mass, more preferably 10 parts by mass to 45 parts by mass. And more preferably 20 to 40 parts by mass. When the content of the plasticizer is 3 parts by mass to 50 parts by mass, it is possible to improve the retention rate of the adhesive strength after the cold and heat cycle test.
  • thickener polymethylmethacrylate, a copolymer of methylmethacrylate and an acrylate ester, a copolymer of methylmethacrylate and another methacrylate ester, acrylic rubber, polyvinyl chloride, polystyrene, Examples thereof include cellulose ester, polyalkyl-2-cyanoacrylic acid ester and ethylene-vinyl acetate copolymer. These thickeners may be used alone or in combination of two or more.
  • the photocurable adhesive composition of the present invention may contain fumed silica.
  • This fumed silica is an ultrafine powder (preferably having a primary particle size of 500 nm or less, particularly preferably 1 nm to 200 nm) anhydrous silica.
  • this anhydrous silica is made from silicon tetrachloride as a raw material and is heated in a flame at high temperature.
  • An ultrafine powder (preferably having a primary particle size of 500 nm or less, particularly preferably 1 nm to 200 nm) anhydrous silica produced due to oxidation in a gas phase, which is hydrophilic silica having high hydrophilicity and hydrophobic silica With highly hydrophobic silica.
  • hydrophobic silicas are preferable because they have good dispersibility in a 2-cyanoacrylate compound.
  • hydrophilic silica various commercially available products can be used, and examples thereof include Aerosil 50, 130, 200, 300 and 380 (these are trade names and 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, 380 ⁇ 30 m 2 / g, respectively.
  • Reorosil QS-10, QS-20, QS-30 and QS-40 (these are trade names, manufactured by Tokuyama Corporation) and the like 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.
  • commercially available hydrophilic silica manufactured by CABOT or the like can also be used.
  • hydrophobic silica a compound capable of reacting with a hydroxy group existing on the surface of the hydrophilic silica to form a hydrophobic group, or adsorbed on the surface of the hydrophilic silica to form a hydrophobic layer on the surface It is possible to use a product produced by treating the surface of the hydrophilic silica by bringing the compound into contact with the hydrophilic silica in the presence or absence of a solvent, preferably by heating.
  • Examples of the compound used for surface-treating hydrophilic silica to make it hydrophobic include alkyl-, aryl-, and aralkyl-based silane coupling agents having a hydrophobic group such as n-octyltrialkoxysilane, methyltrichlorosilane, and dimethyldisilane.
  • Examples thereof include silylating agents such as chlorosilane and hexamethyldisilazane, silicone oils such as polydimethylsiloxane, higher alcohols such as stearyl alcohol, and higher fatty acids such as stearic acid.
  • As the hydrophobic silica a product hydrophobized with any compound may be used.
  • hydrophobic silica examples include Aerosil RY200 and R202, which are surface-treated with silicone oil and hydrophobized, and Aerosil R974, R972, R976, and n-octyltril, which are hydrophobized and surface-treated with a dimethylsilylating agent.
  • Aerosil R805 surface-treated with methoxysilane and hydrophobized Aerosil R811, R812 surface-treated with trimethylsilylating agent and hydrophobized (these are trade names, manufactured by Nippon Aerosil Co., Ltd.) and methyltri Examples include hydrophobically treated Reolosil MT-10 (trade name, manufactured by Tokuyama Corporation) and the like, which is surface-treated with chlorosilane.
  • 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, respectively.
  • / G 150 ⁇ 20 m 2 / g, 260 ⁇ 20 m 2 / g, 120 ⁇ 10 m 2 / g.
  • the preferable content of fumed silica in the photocurable adhesive composition of the present invention is 1 part by mass to 30 parts by mass when the content of the 2-cyanoacrylate compound is 100 parts by mass.
  • the preferred content of the fumed silica depends on the type of the 2-cyanoacrylate compound, the type of the fumed silica, and the like, but 1 part by mass to 25 parts by mass, and particularly preferred content is 2 parts by mass to 20 parts by mass. It is a department.
  • the content of fumed silica is 1 part by mass to 30 parts by mass, it is possible to obtain an adhesive composition having good workability without impairing the curability and adhesive strength of the photocurable adhesive composition. it can.
  • the method for curing the photocurable adhesive composition of the present invention is not particularly limited as long as it can be polymerized and cured by a 2-cyanoacrylate compound, and it can be cured by light or moisture such as moisture. Good.
  • the photocurable adhesive composition of the present invention is cured by light, it is necessary to irradiate ultraviolet rays or visible light using a high pressure mercury lamp, a halogen lamp, a xenon lamp, an LED (light emitting diode) lamp, sunlight or the like. Can be cured.
  • the method for storing the photocurable adhesive composition of the present invention may be carried out by a known storage method, for example, mixing in an atmosphere without or low in humidity and oxygen (for example, 0.01% by volume or less). It is preferable to mix, and it is more preferable to mix under an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. Further, the photocurable adhesive composition of the present invention is preferably stored under light shielding.
  • the photocurable adhesive composition of the present invention can be used as a known 2-cyanoacrylate composition and as a photocurable adhesive composition.
  • it can be used as a so-called instant adhesive, and can also be used as a photocurable instant adhesive.
  • the photocurable adhesive composition of the present invention has photocurability and moisture curability, and since it has excellent storage stability, it can be used in a wide range of fields such as general use, industrial use, and medical use. .
  • sealing of electronic components attachment of reel seats and threading guides on fishing rods, fixing of wire materials such as coils, fixing of magnetic heads to pedestals, and filling used for tooth treatment It can be suitably used for adhesion or fixing between the same or different kinds of articles such as adhesive or artificial nail adhesion or decoration, or coating.
  • Example 1 20 ppm of BF 3 / methanol complex (polymerization inhibitor) in the composition, Sumilizer MDP-S (polymerization inhibitor, the following compound) in the composition was 1,000 ppm, Ferrocene (FeCp 2 , Group 8 transition metal metallocene compound, manufactured by Wako Pure Chemical Industries, Ltd.) in the composition of 600 ppm, 3,000 ppm in the composition of Ivocerin (photoradical generator, the following compound, manufactured by Ivoclar Vivadent) So as to obtain a photocurable adhesive composition of Example 1 by mixing with an acid content (acid content) of 0.20 ⁇ g equivalent of 2-octyl ester of 2-cyanoacrylic acid (2-OctCA).
  • the obtained photocurable adhesive composition was placed in a light-tight sealed container and stored in a thermostatic chamber at 60 ° C., and the photocurable adhesive composition at the initial and elapsed time points shown in Table 1 was taken and polyethylene was used. A liquid film having a thickness of 1 mm was formed in the container. This was irradiated with an intensity of 150 W / cm 2 (wavelength 405 nm value) using a spot type UV irradiation device (Spot Cure UIS-25102 manufactured by Ushio Inc.) equipped with a long pass filter (GG395 manufactured by Schott). The irradiation time until the sample was completely cured was measured.
  • Example 7 and Comparative Example 5 were not equipped with a long pass filter, and were similarly irradiated with 150 W / cm 2 (UV-A: a value at a wavelength of 320 nm to 390 nm). The smaller the value, the better the photocurability.
  • UV-A a value at a wavelength of 320 nm to 390 nm. The smaller the value, the better the photocurability.
  • Table 1 The evaluation results are shown in Table 1.
  • Example 1 Example 1 except that 1,4-hydroquinone (HQ), 1,4-benzoquinone (BQ) and 2-hydroxy-1,4-naphthoquinone were added to the composition in the amounts shown in Table 1.
  • Photocurable adhesive compositions were prepared in the same manner as in. Using the obtained photocurable adhesive composition, various evaluations were performed in the same manner as in Example 1. The evaluation results are summarized in Table 1.
  • Example 6 to 8 and Comparative Examples 3 to 5 An acid content (acid content) of 0.62 ⁇ g equivalent of 2-octyl ester of 2-cyanoacrylic acid (2-OctCA) was used. Instead of Ivocerin, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (iGM, trade name "Omnirad819”) or 2,2-dimethoxy-2-phenylacetone (iGM, trade name "Omnirad651”) was added to the composition in the amounts shown in Table 2. In the same manner as in Example 1, a photocurable adhesive composition was prepared. Using the obtained photocurable adhesive composition, various evaluations were performed in the same manner as in Example 1. The evaluation results are summarized in Table 2.
  • Example 9 to 11 and Comparative Examples 6 and 7 2-OctCA is changed to 2-ethoxyethyl ester of 2-cyanoacrylic acid (EtOEtCA), and the contents of ferrocene (FeCp 2 , group transition metal metallocene compound) and Ivocerin (photoradical generator) are shown in Table 3.
  • ferrocene FeCp 2 , group transition metal metallocene compound
  • Ivocerin photoradical generator
  • Example 12 to 14 and Comparative Examples 8 and 9 2-OctCA was changed to isobutyl ester of 2-cyanoacrylic acid (iBuCA), and the contents of ferrocene (FeCp 2 , Group 8 transition metal metallocene compound) and Ivocerin (photoradical generator) were the amounts shown in Table 4.
  • ferrocene FeCp 2 , Group 8 transition metal metallocene compound
  • Ivocerin photoradical generator
  • the photocurable adhesive compositions of Examples which are the photocurable adhesive compositions of the present invention, are more storage stable than the photocurable adhesive compositions of Comparative Examples. Excellent in.

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

Abstract

La composition d'adhésif photodurcissable de l'invention comprend un composé métallocène de métal de transition du groupe 8 et un composé 2-cyanoacrylate, et ne comprend pas de composé possédant une structure benzoquinone, ou présente une teneur en composé possédant une structure benzoquinone supérieure à ０ｐｐｍ et inférieure à ４ｐｐｍ.
PCT/JP2019/041399 2018-10-23 2019-10-21 Composition d'adhésif photodurcissable Ceased WO2020085334A1 (fr)

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EP3960151A1 (fr) * 2020-08-27 2022-03-02 Cuantum Medical Cosmetics, S.L. Composition de cyanoacrylate photodurcissable à exotherme contrôlé
WO2022187848A1 (fr) * 2021-03-05 2022-09-09 H.B. Fuller Company Composition de cyanoacrylate avec stabilisant sans danger
JP2022139218A (ja) * 2021-03-11 2022-09-26 東亞合成株式会社 端子付き電線、ワイヤーハーネス、端子付き電線の製造方法及び硬化性組成物
WO2025047585A1 (fr) * 2023-08-31 2025-03-06 東亞合成株式会社 Procédé de production d'un corps assemblé
WO2025058006A1 (fr) * 2023-09-15 2025-03-20 東亞合成株式会社 Composition adhésive photodurcissable, corps lié et composition de 2-cyanoacrylate pour adhésif photodurcissable
EP4567051A1 (fr) * 2023-12-04 2025-06-11 Bostik SA Composition photodurcissable comprenant du n-heptylcyanoacrylate, du n-hexylcyanoacrylate ou du n-octylcyanoacrylate

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EP3960151A1 (fr) * 2020-08-27 2022-03-02 Cuantum Medical Cosmetics, S.L. Composition de cyanoacrylate photodurcissable à exotherme contrôlé
WO2022187848A1 (fr) * 2021-03-05 2022-09-09 H.B. Fuller Company Composition de cyanoacrylate avec stabilisant sans danger
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JP2022139218A (ja) * 2021-03-11 2022-09-26 東亞合成株式会社 端子付き電線、ワイヤーハーネス、端子付き電線の製造方法及び硬化性組成物
WO2025047585A1 (fr) * 2023-08-31 2025-03-06 東亞合成株式会社 Procédé de production d'un corps assemblé
WO2025058006A1 (fr) * 2023-09-15 2025-03-20 東亞合成株式会社 Composition adhésive photodurcissable, corps lié et composition de 2-cyanoacrylate pour adhésif photodurcissable
EP4567051A1 (fr) * 2023-12-04 2025-06-11 Bostik SA Composition photodurcissable comprenant du n-heptylcyanoacrylate, du n-hexylcyanoacrylate ou du n-octylcyanoacrylate
WO2025119863A1 (fr) * 2023-12-04 2025-06-12 Bostik Sa Composition photodurcissable comprenant du cyanoacrylate de n-heptyle, du cyanoacrylate de n-hexyle ou du cyanoacrylate de n-octyle

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