CN114390970A - Actinic ray pre-irradiation curing method for actinic ray-curable anaerobic adhesive - Google Patents
Actinic ray pre-irradiation curing method for actinic ray-curable anaerobic adhesive Download PDFInfo
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- CN114390970A CN114390970A CN201980100401.5A CN201980100401A CN114390970A CN 114390970 A CN114390970 A CN 114390970A CN 201980100401 A CN201980100401 A CN 201980100401A CN 114390970 A CN114390970 A CN 114390970A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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Abstract
The present invention relates to a curing method for an actinic ray-curable anaerobic adhesive, comprising the steps of: a) providing a first substrate; b) applying an actinic ray curable anaerobic adhesive to a surface of the first substrate; c) irradiating the anaerobic adhesive with actinic radiation for a pre-irradiation time that is 20% to 60% of the actinic radiation cure time of the actinic radiation curable anaerobic adhesive measured at the same actinic radiation and intensity; d) laying a second substrate over the first substrate such that the actinic ray-curable anaerobic adhesive is between the first substrate and the second substrate, and curing the actinic ray-curable anaerobic adhesive under anaerobic conditions. The actinic ray-curable anaerobic adhesive cured by the curing method has a shortened set time under anaerobic conditions.
Description
Technical Field
The present invention relates to a curing method for an actinic ray-curable anaerobic adhesive, comprising the steps of: a) providing a first substrate; b) applying an actinic ray curable anaerobic adhesive to a surface of the first substrate; c) irradiating the actinic ray-curable anaerobic adhesive with actinic rays for a pre-irradiation time that is 20% to 60% of the curing time of the actinic ray-curable anaerobic adhesive measured at the same actinic ray and intensity; d) laying a second substrate over the first substrate such that the actinic ray-curable anaerobic adhesive is between the first substrate and the second substrate, and curing the actinic ray-curable anaerobic adhesive under anaerobic conditions. The actinic ray-curable anaerobic adhesive cured by the curing method of the present invention has a shortened set time (fix time) under anaerobic conditions.
Background
Anaerobic adhesives have been widely used for structural bonding of metals, glass and plastics. Typical uses for anaerobic adhesives include, but are not limited to, enhancing sealing or preventing screw loss. One disadvantage of current anaerobic adhesives is that it takes a long time to cure, and therefore it has a negative impact on the work efficiency of the operator.
Therefore, there is a need to develop a curing method for an actinic ray-curable anaerobic adhesive to shorten the fixing time and simplify its working process.
Disclosure of Invention
The present invention relates to a curing method for an actinic ray-curable anaerobic adhesive, comprising the steps of:
a) providing a first substrate;
b) applying an actinic ray curable anaerobic adhesive to a surface of the first substrate;
c) irradiating the actinic ray-curable anaerobic adhesive with actinic rays for a pre-irradiation time that is 20% to 60% of the actinic ray curing time of the actinic ray-curable anaerobic adhesive measured at the same actinic ray and intensity;
d) laying a second substrate over the first substrate such that the actinic ray-curable anaerobic adhesive is between the first substrate and the second substrate, and curing the actinic ray-curable anaerobic adhesive under anaerobic conditions.
The actinic ray-curable anaerobic adhesive cured by the curing method of the present invention has a shortened set time compared to a usual anaerobic cure time.
The present invention also relates to an actinic ray-curable anaerobic adhesive cured by the curing method of the present invention.
The present invention also relates to articles bonded by the actinic ray-curable anaerobic adhesive cured by the curing method of the present invention.
Detailed Description
The invention is described in more detail in the following paragraphs. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In the context of the present invention, the terms used will be construed according to the following definitions, unless the context indicates otherwise.
As used herein, the singular forms "a", "an" and "the" include both singular and plural referents unless the context clearly dictates otherwise.
As used herein, the terms "comprising" and "consisting of … …" are synonymous with "including" or "containing" and are inclusive or open-ended and do not exclude additional, unrecited elements, components, or process steps.
The recitation of numerical endpoints includes all numbers and fractions within the corresponding range, and the recited endpoints.
All references cited in this specification are incorporated by reference in their entirety.
Unless defined otherwise, all terms used in disclosing the invention, including technical and scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, definitions of terms are included to better understand the teachings of the present invention.
In the context of the present disclosure, a number of the following terms will be utilized.
The term "acrylate" refers to both or either of "acrylate" and "methacrylate".
The term "acrylic" refers to both or either of "acrylic" and "methacrylic".
The term "optionally substituted monovalent hydrocarbon group" means an optionally substituted alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, tert-butyl, isobutyl, chloromethyl, 3,3, 3-trifluoropropyl, and the like; optionally substituted alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, and the like; optionally substituted aralkyl groups such as benzyl, phenethyl, 2- (2,4, 6-trimethylphenyl) propyl and the like; or optionally substituted aryl groups such as phenyl, tolyl, xylyl (xyxyl), and the like.
The term "optionally substituted divalent hydrocarbon group" refers to optionally substituted alkylene, alkenylene (alkenylene group), alkynylene (alklylene group), cycloalkylene (cycloalkylene group), arylene (arylene group), and the like.
The term "ethylenically unsaturated" refers to at least one site of non-aromatic unsaturation.
The term "anaerobic cure time" refers to the cure time of an actinic ray-curable anaerobic adhesive that is cured under anaerobic conditions without involving an actinic ray pre-irradiation step described by the curing method of the present invention.
The term "actinic ray curing time" refers to the curing time of an actinic ray-curable anaerobic adhesive which is cured under irradiation of actinic rays.
The term "pre-irradiation time" refers to the time at which the curing of the actinic ray-curable anaerobic adhesive is initiated under irradiation of actinic rays. During the pre-irradiation time, the actinic ray-curable anaerobic adhesive begins to cure, but fails to fully cure. The pre-irradiation time of the present invention is shorter than or equal to the actinic ray curing time.
The term "fixed time" refers to the curing time of an actinic ray-curable anaerobic adhesive that has been pre-irradiated, which is cured under anaerobic conditions.
The present invention relates to a curing method for an actinic ray-curable anaerobic adhesive, comprising the steps of:
a) providing a first substrate;
b) applying an actinic ray curable anaerobic adhesive to a surface of the first substrate;
c) irradiating the actinic ray-curable anaerobic adhesive with actinic rays for a pre-irradiation time that is 20% to 60% of the actinic ray curing time of the actinic ray-curable anaerobic adhesive measured at the same actinic ray and intensity; and
d) laying a second substrate over the first substrate such that the actinic ray-curable anaerobic adhesive is between the first substrate and the second substrate, and curing the actinic ray-curable anaerobic adhesive under anaerobic conditions.
The curing method of the present invention utilizes actinic radiation to first initiate curing of the actinic radiation curable anaerobic adhesive. It is crucial to control the pre-irradiation time to about 20% to 60% of the actinic ray curing time of the actinic ray-curable anaerobic adhesive measured at the same actinic ray and intensity. After assembling the first and second substrates, the actinic ray-curable anaerobic adhesive is further cured under anaerobic conditions. It has surprisingly been found that by using the curing method of the present invention, the fixing time of the actinic ray-curable anaerobic adhesive is significantly shorter than the anaerobic curing time.
In some embodiments of the present invention, the pre-irradiation time is preferably 30% to 50%, and more preferably 35% to 50% of the actinic ray curing time of the actinic ray-curable anaerobic adhesive measured at the same actinic ray and intensity.
First and second substrates
The first substrate and the second substrate of the present invention are bonded by an actinic ray curable anaerobic adhesive. The first substrate and the second substrate may be the same or different and are independently selected from, for example, a metal substrate, an alloyed substrate, a plastic substrate, or a wooden substrate. The assembly of the first substrate with the second substrate will create an anaerobic environment for curing the actinic ray curable anaerobic adhesive.
In some embodiments of the present invention, the first substrate and the second substrate are preferably cleaned prior to applying the actinic radiation curable anaerobic adhesive. The metal substrate is preferably treated with isopropanol, ethanol or ethyl acetate and the wood or plastic substrate is preferably blown by compressed air.
In some embodiments of the invention, at least one of the first substrate and the second substrate is preferably a non-actinic ray transmissive substrate. More preferably, both the first substrate and the second substrate are non-actinic ray transmissive substrates. The curing method of the present invention is particularly useful when both the first substrate and the second substrate are non-actinic ray transmissive substrates, because actinic rays do not contribute to the curing of the actinic ray curable anaerobic adhesive after the first substrate and the second substrate are assembled together. Typical applications for the curing method of the present invention include, but are not limited to, facilitating the curing of actinic ray curable anaerobic adhesives for thread locking, sealing and positioning.
Anaerobic adhesive
The actinic ray-curable anaerobic adhesive of the present invention may be any actinic ray-curable anaerobic adhesive known in the art, and generally comprises:
a) at least one ethylenically unsaturated monomer;
b) at least one photoinitiator;
c) at least one redox initiator; and
d) at least one stabilizer.
< ethylenically unsaturated monomer >
The ethylenically unsaturated monomer of the present invention means any ethylenically unsaturated monomer capable of radical polymerization and containing at least one group having the following general formula (1):
in formula (1), R represents hydrogen, halogen, or optionally substituted C1To C20A monovalent hydrocarbon group. Preferably, R is hydrogen or optionally substituted C1To C8A monovalent hydrocarbon group. More preferably, R is hydrogen or methyl.
Examples of ethylenically unsaturated monomers include, but are not limited to, isobornyl acrylate (IBOA), isobornyl methacrylate (IBOMA), cyclohexyl acrylate, cyclohexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, t-butylcyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, phenethylacrylate, phenethylmethacrylate, dicyclopentyl acrylate, 3, 5-trimethylcyclohexyl methacrylate, dicyclopentenyl acrylate, 1, 6-hexanediol diacrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, isooctyl acrylate, n-dodecyl acrylate, n-tridecyl acrylate, n-hexadecyl acrylate, n-octadecyl acrylate, iso-tetradecyl acrylate, and iso-octadecyl acrylate. The ethylenically unsaturated monomers may be used alone or in any combination.
Examples of commercially available ethylenically unsaturated monomers are, for example, IBOMA from KPX, THFMA (tetrahydrofurfuryl methacrylate), PhEMA (phenoxyethyl methacrylate), IBOA, EHMA (ethylene glycol dimethacrylate); TEGDMA (triethylene glycol dimethacrylate) from Satomer; and DHMA (ethylene glycol dimethacrylate) from BASF.
In some embodiments of the present invention, the amount of the ethylenically unsaturated monomer is 5 to 90 wt%, preferably 5 to 70 wt%, and more preferably 30 to 70 wt%, based on the total weight of the actinic ray-curable anaerobic adhesive.
< photoinitiator >
The photoinitiator of the present invention refers to any common photoinitiator known in the art, and preferably comprises at least one radical photoinitiator, for example selected from benzophenone, acetophenone, chlorinated acetophenone, dialkoxyacetophenone, dialkyl hydroxyacetophenone ester, benzoin acetate, benzoin alkyl ether, dimethoxybenzoin, dibenzylketone, benzoylcyclohexanol and other aromatic ketones, acyloxime ester, acylphosphine oxide phosphate (acylphospholine oxides), acylphosphonate (acylphosphine oxides), ketone sulfide (ketosulfines), dibenzoyl disulfide (dibenzoyldisulfide), diphenyldithiocarbonate and diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide. Photoinitiators can be used alone or in any combination.
Examples of commercially available photoinitiators include, but are not limited to, Irgacure 184, Irgacure 500, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 1700, Irgacure 651, Irgacure 819, Irgacure 1000, Irgacure 1300, Irgacure1870, Darocur 1173, Darocur 2959, Darocur 4265, and Darocur TPO from Ciba Specialty Chemicals; lucerin TPO from BASF AG; esacure KT046, Esacure KIP150, EsacureKT37, and Esacure EDB from LAMBERTI; H-Nu 470 and H-Nu 470X from SPECTRA GROUP Ltd; and Genopol TX-1 from Rahn AG.
In some embodiments of the present invention, the amount of the photoinitiator is 0.1 to 8 wt%, preferably 0.5 to 5 wt%, and more preferably 3 to 5 wt%, based on the total weight of the actinic ray-curable anaerobic adhesive.
< Redox initiator >
The redox initiators of the present invention are useful for initiating polymerization that relies on free radicals generated during redox reactions under anaerobic conditions. And the initiator may be selected from peroxide initiators such as Cumene Hydroperoxide (CHP), acetyl peroxide, dicumyl peroxide (DCP), 2, 5-dimethyl-2, 5-di (t-butylperoxy) -hexyne (DBPH), Benzoyl Peroxide (BPO), 2, 4-dichlorobenzoyl peroxide (DCBP), t-butyl peroxypivalate (BPP), dicyclohexyl peroxydicarbonate (DCPD), potassium persulfate (KSP), ammonium persulfate (ASP), etc.; azo compound initiators such as 2,2 '-azo-bis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azo-bis-isobutyronitrile, azobisisoheptonitrile, and the like; and persulfate initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, and the like. The redox initiators may be used alone or in any combination. Preferably, a peroxide initiator is used.
Examples of commercially available redox initiators are, for example, BPO and CHP from the national drug group; and VAZO 52 and VAZO 67 from DuPont Chemical.
In some embodiments of the present invention, the amount of the redox initiator is 0.2 to 10 wt%, preferably 0.5 to 5 wt%, and more preferably 1 to 5 wt%, based on the total weight of the actinic ray-curable anaerobic adhesive.
< stabilizers >
The stabilizer of the present invention refers to any of the common acid polymerization inhibitors and free radical inhibitors known in the art. Examples of stabilizers include, but are not limited to, sulfur dioxide, glacial acetic acid, hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, tert-butylcatechol, butylated hydroxytoluene, 4-methoxyphenol, 2, 6-di-tert-butylphenol, and the like. The stabilizers may be used alone or in any combination.
Examples of commercially available stabilizers are e.g. Butylated Hydroxytoluene (BHT) from the national drug group; ethylenediaminetetraacetic acid tetrasodium salt from Bhakti Chemical (EDTA-Na 4); p-benzoquinone from Yu Ming, shanghai; and hydroxyethane-1, 1-diphosphonic acid from Rhodia.
In some embodiments of the present invention, the amount of the stabilizer is 0.005 to 5 wt%, preferably 0.01 to 1 wt%, and even more preferably 0.01 to 0.2 wt%, based on the total weight of the actinic ray-curable anaerobic adhesive.
< optional additives >
At least one adhesion promoter may additionally be present in the actinic ray-curable anaerobic adhesive to enhance its adhesive strength. The adhesion promoter may be any adhesion promoter known in the art and is preferably a phosphorus-containing compound having ethylenic unsaturation. More preferably, the phosphorus-containing compound having ethylenic unsaturation is a (meth) acrylate functionalized phosphate ester having the following general formula (2):
in the above formula (2), R1、R2And R3May be the same or different and may be independently selected from hydrogen or general formula (3).
In the above formula (3), R represents1、R2Or R3A bonding position to the oxygen atom in formula (2); r4Selected from hydrogen or optionally substituted C1To C8A monovalent hydrocarbon group, and preferably hydrogen or methyl; a represents optionally substituted C1To C8A divalent hydrocarbon group, and preferably C2To C4An alkylene group.
Specific non-limiting examples of phosphate esters of (meth) acrylates suitable for use in the present invention are:
commercially available adhesion promoters include, but are not limited to, Ebecryl 168, Ebecryl 170, and Ebecryl 171 from Allnex; kayamer PM-2 and Kayamer PM-21 from Nippon Kayaku co.Ltd; genorad 40 from Rahn; SR9050, SR9051 and SR9054 from Arkema; and PAM100 and PAM200 from Rodia.
At least one ethylenically unsaturated carboxylic acid may be additionally present in the actinic ray-curable anaerobic adhesive to accelerate the curing process. Preferably, the ethylenically unsaturated carboxylic acid is in a (meth) acrylate terminated form. Examples of ethylenically unsaturated carboxylic acids include, but are not limited to, acrylic acid, maleic acid (maleic acid), itaconic acid, crotonic acid (crotonoic acid), and fumaric acid. The ethylenically unsaturated carboxylic acids of the present invention may be used alone or in any combination. Examples of commercially available ethylenically unsaturated carboxylic acids are, for example, methacrylic acid (MAA) from the national pharmaceuticals group.
At least one saccharin or saccharin derivative or Acetophenylhydrazine (APH) may additionally be present in the actinic ray-curable anaerobic adhesive to promote curing on low-active surfaces. Saccharin derivatives include any known metal salts of saccharin, such as the sodium, potassium, and copper salts resulting from the reaction of saccharin with a metal or metathesis with a metal salt. Examples of commercially available saccharin or saccharin derivatives are, for example, saccharin from Sigma Aldrich.
At least one acrylic resin may be additionally present in the actinic ray-curable anaerobic adhesive. The acrylic resin may be obtained by polymerization of one or more acrylic monomers; optionally, it may be obtained by polymerization of one or more acrylic monomers in combination with non-acrylic monomers. Exemplary acrylic oligomers include poly (methyl methacrylate), poly (ethyl methacrylate), poly (methyl methacrylate/n-butyl acrylate/ethyl acrylate), poly (n-butyl methacrylate/isobutyl methacrylate), poly (n-butyl methacrylate), poly (ethyl methacrylate), and combinations thereof. Examples of commercially available acrylic resins are, for example, CN959 from Sartomer.
Other optional additives that may be used in the actinic radiation curable anaerobic adhesive of the present invention include, but are not limited to, cross-linking agents; an enhancer; a filler; a pigment; a thickener; a solvent; and mixtures thereof.
In a preferred embodiment, the actinic ray-curable anaerobic adhesive comprises:
5 to 70 weight percent of at least one ethylenically unsaturated monomer;
0.5 to 5% by weight of at least one photoinitiator;
0.5 to 3 wt% of at least one redox initiator;
0.01 to 1% by weight of at least one stabilizer;
0.1 to 3% by weight of at least one adhesion promoter;
0 to 8% by weight of at least one ethylenically unsaturated carboxylic acid;
0.2 to 3% by weight of at least one saccharin, and/or saccharin derivative, and/or APH; and
30 to 90% by weight of at least one acrylic resin;
wherein the weight percentages of all components add up to 100 weight%.
The actinic ray-curable anaerobic adhesive can be prepared by uniformly mixing all the components, and is preferably prepared under yellow light.
Actinic ray
The actinic radiation of the present invention should have sufficient energy to initiate the polymerization or crosslinking reaction. Actinic radiation includes, but is not limited to, alpha-rays, gamma-rays, ultraviolet radiation (UV), visible light, and electron beams. The actinic rays preferably have 30mW/cm2To 500mW/cm2More preferably 50mW/cm2To 150mW/cm2And even more preferably 50mW/cm2To 100mW/cm2The energy of (a).
In some embodiments of the present invention, UV radiation and electron beam are preferably used for pre-irradiation of the actinic ray curable anaerobic adhesive. More preferably, UV radiation is selected as the energy source for pre-irradiation of the actinic ray curable anaerobic adhesive. The UV radiation preferably has a wavelength of 240nm to 410nm, and more preferably has a wavelength of 320nm to 400 nm. Representative examples of UV radiation sources include LED UV curing equipment (model 97070, from Loctite Henkel), and Fusion UV equipment (LH6BPS, from Fusion UV System Inc.).
In a preferred embodiment of the present invention, the curing method for the actinic ray-curable anaerobic adhesive includes the steps of:
a) providing a precleaned first substrate;
b) applying an actinic ray curable anaerobic adhesive to a surface of the first substrate;
c) with a density of 30mW/cm2To 500mW/cm2Irradiating the actinic ray-curable anaerobic adhesive with UV radiation of an energy and a wavelength of 240nm to 410nm for a pre-irradiation time that is 20% to 60% of the actinic ray curing time of the actinic ray-curable anaerobic adhesive measured at the same UV radiation and intensity; and
d) laying a precleaned second substrate over the first substrate such that the actinic ray-curable anaerobic adhesive is between the first substrate and the second substrate, and curing the actinic ray-curable anaerobic adhesive under anaerobic conditions.
Examples
The present invention will be described and illustrated in further detail with reference to the following examples. These examples are intended to assist those skilled in the art in better understanding and practicing the present invention, and are not intended, however, to limit the scope of the present invention. All numbers in the examples are on a weight basis unless otherwise indicated.
Test method
Three different kinds of actinic rays were used in the test of the present invention, including a wavelength of 405nm and an intensity of 320mW/cm2With a wavelength of 375nm and an intensity of70mW/cm2And an Hg lamp (UVA: 60 mW/cm)2；UVB：55mW/cm2；UVC：14mW/cm2(ii) a And UVV: 45mW/cm2). The test methods described below can be applied to all tests using the three actinic rays.
< actinic ray curing time >
Actinic ray cure time is determined by measuring the time to fix two slides bonded by an actinic ray curable anaerobic adhesive that is exposed to actinic rays at room temperature. A turning moment of about 5N × m is applied to the slide. At the time when the two glass slides were not relatively moved, the time was recorded as the actinic ray curing time of the actinic ray-curable anaerobic adhesive.
< fixing time >
Two galvanized steel sheets were first pre-wiped with isopropanol. An actinic ray-curable anaerobic adhesive is applied to one of the galvanized steel sheets and the galvanized steel sheet is placed in a chamber equipped with a source of actinic radiation. The actinic ray-curable anaerobic adhesive is irradiated for a period of time less than or equal to the actinic ray curing time. Then, the galvanized steel sheet is taken out of the chamber, and another galvanized steel sheet is placed on top of the galvanized steel sheet to which the actinic ray-curable anaerobic adhesive is applied, thereby forming an anaerobic environment for the actinic ray-curable anaerobic adhesive to be further cured at room temperature.
The fixing time was determined by measuring the time during which the adhesive bond formed by the actinic ray-curable anaerobic adhesive that had been pre-irradiated could support a tensile force of 3kg for 5 seconds without breaking. The 3kg tension was applied parallel to the long axis of the bonded area and the galvanized steel sheet.
< anaerobic curing time >
Two galvanized steel sheets were first pre-wiped with isopropyl alcohol. An actinic ray-curable anaerobic adhesive is applied to one of the galvanized steel sheets, and the other galvanized steel sheet is placed on top of the galvanized steel sheet to which the actinic ray-curable anaerobic adhesive is applied, thereby forming an anaerobic environment for the actinic ray-curable anaerobic adhesive to be further cured at room temperature.
The anaerobic curing time was determined by measuring the time for which the adhesive bond formed by the actinic ray-curable anaerobic adhesive can support a tensile force of 3kg for 5 seconds without breaking. The 3kg tension was applied parallel to the long axis of the bonded area and the galvanized steel sheet.
Examples 1 to 3
The following materials were used in the examples.
HEMA (2-hydroxyethyl methacrylate from Wittiness);
saccharin (from Sigma Aldrich);
APH (acetyl-2-phenylhydrazine from GP Chemicals);
CN959 (aliphatic urethane oligomer from Sartomer);
p-benzoquinone (from Shanghai Yu Ming);
EDTA-Na4 (tetrasodium salt of ethylenediaminetetraacetic acid from Bhakti Chemical);
hydroxyethane-1, 1-diphosphonic acid (from Rhodia);
kayamer PM2 (bis (2-methacryloyloxyethyl) phosphate from Nippon Kayaku);
cumene hydroperoxide (from Sasol);
acrylic acid (from dow chemical);
irgacure 184 (from IMG Resins),
irgacure 819 (from IMG Resins); and
darocur TPO (from Ciba Specialty Chemicals).
An actinic ray-curable anaerobic adhesive was prepared as in example (Ex.) and formulated by thoroughly mixing all the components according to the components and amounts in table 1.
TABLE 1 actinic ray-curable anaerobic adhesives
The test results are reported in tables 2A to 2C. It has been shown that when the pre-irradiation time is controlled to be about 20% to 60% of the actinic ray curing time of the actinic ray-curable anaerobic adhesive measured at the same actinic ray and intensity, the fixing time is significantly shorter than the anaerobic curing time of the actinic ray-curable anaerobic adhesive. In contrast, when the pre-irradiation time is too long, the fixing time of the actinic ray-curable anaerobic adhesive can be even longer than the anaerobic curing time.
Table 2A test results of example 1
Table 2B test results of example 2
Table 2C test results of example 3
Claims (11)
1. A curing process for an anaerobic adhesive comprising the steps of:
a) providing a first substrate;
b) applying an actinic ray curable anaerobic adhesive to a surface of the first substrate;
c) irradiating the actinic ray-curable anaerobic adhesive with actinic rays for a pre-irradiation time that is 20% to 60% of the actinic ray curing time of the actinic ray-curable anaerobic adhesive measured at the same actinic ray and intensity; and
d) laying a second substrate over the first substrate such that the actinic ray-curable anaerobic adhesive is between the first substrate and the second substrate, and curing the actinic ray-curable anaerobic adhesive under anaerobic conditions.
2. The curing method of claim 1, wherein at least one of the first substrate and the second substrate is a non-actinic-ray transmissive substrate, and preferably both the first substrate and the second substrate are non-actinic-ray transmissive substrates.
3. The curing method according to claim 1 or 2, wherein the actinic ray-curable anaerobic adhesive preferably comprises:
a) at least one ethylenically unsaturated monomer;
b) at least one photoinitiator;
c) at least one redox initiator; and
d) at least one stabilizer.
4. The curing process of claim 3, wherein the redox initiator is preferably a peroxide initiator.
5. The curing process of claim 3, wherein the actinic ray-curable anaerobic adhesive additionally comprises at least one adhesion promoter, and/or at least one saccharin or saccharin derivative, and/or at least one APH, and/or at least one acrylic resin, and/or at least one ethylenically unsaturated carboxylic acid.
6. The curing process according to any one of the preceding claims, wherein the actinic radiation preferably has 30mW/cm2To 500mW/cm2More preferably 50mW/cm2To 150mW/cm2And even more preferably 50mW/cm2To 100mW/cm2The energy of (a).
7. The curing process according to any one of the preceding claims, wherein the actinic radiation is preferably UV radiation or electron beam, and more preferably UV radiation.
8. The curing process according to any one of the preceding claims, wherein the wavelength of the actinic radiation light is preferably from 240nm to 410nm, and more preferably from 320nm to 400 nm.
9. The curing method of any preceding claim, wherein the pre-irradiation time is preferably 30% to 50%, and more preferably 35% to 50% of the actinic ray curing time of the actinic ray curable anaerobic adhesive measured at the same actinic ray and intensity.
10. An actinic ray-curable anaerobic adhesive cured according to any one of the preceding claims.
11. An article bonded by the actinic ray curable anaerobic adhesive according to claim 10.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2019/106394 WO2021051301A1 (en) | 2019-09-18 | 2019-09-18 | Actinic ray pre-illumination curing method for actinic ray curable anaerobic adhesives |
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| CN (1) | CN114390970A (en) |
| WO (1) | WO2021051301A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739963A2 (en) * | 1995-04-25 | 1996-10-30 | Cemedine Co., Ltd. | Rapid curing adhesion method |
| WO2001051576A1 (en) * | 2000-01-11 | 2001-07-19 | Loctite (R & D) Limited | Acrylic adhesive compositions containing ketonyl (meth)acrylate |
| WO2007120630A2 (en) * | 2006-04-10 | 2007-10-25 | Abm Associates Llc | Activated anaerobic adhesive and use thereof |
| US20080251195A1 (en) * | 2007-04-10 | 2008-10-16 | Abm Associates Llc | Activated anaerobic adhesive and use thereof |
| CN110128994A (en) * | 2019-04-09 | 2019-08-16 | 中海油常州涂料化工研究院有限公司 | A kind of anaerobic adhesive of moisture-curable and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205451B (en) * | 2007-11-30 | 2011-04-27 | 华南理工大学 | Ultraviolet-anaerobic dual curing adhesive |
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2019
- 2019-09-18 WO PCT/CN2019/106394 patent/WO2021051301A1/en active Application Filing
- 2019-09-18 CN CN201980100401.5A patent/CN114390970A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739963A2 (en) * | 1995-04-25 | 1996-10-30 | Cemedine Co., Ltd. | Rapid curing adhesion method |
| WO2001051576A1 (en) * | 2000-01-11 | 2001-07-19 | Loctite (R & D) Limited | Acrylic adhesive compositions containing ketonyl (meth)acrylate |
| WO2007120630A2 (en) * | 2006-04-10 | 2007-10-25 | Abm Associates Llc | Activated anaerobic adhesive and use thereof |
| US20080251195A1 (en) * | 2007-04-10 | 2008-10-16 | Abm Associates Llc | Activated anaerobic adhesive and use thereof |
| CN110128994A (en) * | 2019-04-09 | 2019-08-16 | 中海油常州涂料化工研究院有限公司 | A kind of anaerobic adhesive of moisture-curable and preparation method thereof |
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| Publication number | Publication date |
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| WO2021051301A1 (en) | 2021-03-25 |
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