Classifications

• • 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
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides

Definitions

• the present invention relates to an anaerobic adhesive composition.
• Saccharin can exhibit sufficient function as an anaerobic curing accelerator in an anaerobic adhesive composition.
• an anaerobic adhesive composition may require a composition suitable for its application, and from the viewpoint of freedom of composition, a new anaerobic curing accelerator is desired.
• An object of one aspect of the present invention is to provide an anaerobic adhesive composition containing a new component that functions as an anaerobic curing accelerator in the anaerobic adhesive composition.
• an anaerobic adhesive composition contains a (meth)acrylic monomer, an organic peroxide and an anaerobic curing accelerator, Curing accelerators include certain hydroquinone-based compounds and benzoquinone.
• anaerobic adhesive composition containing a new component that functions as an anaerobic curing accelerator in the anaerobic adhesive composition.
• the anaerobic adhesive composition according to the embodiment of the present invention contains a (meth)acrylic monomer, an organic peroxide and an anaerobic curing accelerator.
• (meth)acrylic or “(meth)acrylate” is a generic term for acrylic and methacrylic, or a generic term for acrylate and methacrylate, and means one or both of them.
• "to” means a range including the numerical values at both ends (more than or equal to or less than).
• Examples of (meth)acrylic monomers include (meth)acrylic acid, (meth)acrylic acid alkyl esters, phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (Meth)acrylic acid hydroxyalkyl esters such as isobornyl (meth)acrylate and hydroxyethyl acrylate, poly(meth)acrylates of polyhydric alcohols, and epoxy (meth)acrylates obtained by adding (meth)acrylic acid to epoxy resins. , urethane poly(meth)acrylates, polyester poly(meth)acrylates, and di(meth)acrylates of alkylene oxide adducts of bisphenol A, such as ethoxylated bisphenol A dimethacrylate.
• Examples of (meth)acrylic monomers include acidic phosphate esters containing (meth)acryloyloxy groups.
• esters include mono(meth)acryloyloxyethyl phosphate such as mono(2-hydroxyethyl methacrylate) phosphate, di(meth)acryloyloxyethyl phosphate, mono(meth)acryloyloxypropyl phosphate, di(meth)acryloyl Included are oxypropyl phosphate, mono(meth)acryloyloxy- ⁇ -chloropropyl phosphate and di(meth)acryloyloxy- ⁇ -chloropropyl phosphate.
• the (meth)acrylic monomer is the main component in the anaerobic adhesive composition according to the embodiment of the present invention.
• the content of components other than the (meth)acrylic monomer in the anaerobic adhesive composition can be appropriately determined based on the amount of the (meth)acrylic monomer.
• Organic peroxides function as initiators for radical polymerization of (meth)acrylic monomers. One or more organic peroxides may be used.
• organic peroxides examples include ketone peroxides, dialkyl peroxides, diacyl peroxides, peroxyesters and hydroperoxides, among which hydroperoxides are used in anaerobic adhesive compositions. from the viewpoint of curability and storage stability.
• hydroperoxides include tertiarybutyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide and paramenthane hydroperoxide.
• the content of the organic peroxide in the anaerobic adhesive composition is preferably 0.05 parts by mass or more per 100 parts by mass of the (meth)acrylic monomer. It is more preferably 1 part by mass or more. From the viewpoint of further enhancing the storage stability of the anaerobic adhesive composition, the amount is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
• the anaerobic curing accelerator accelerates the curing of the anaerobic adhesive composition by shortening the curing time of the anaerobic adhesive composition or accelerating the curing reaction in an anaerobic environment. is an ingredient.
• One or more anaerobic curing accelerators may be used.
• the anaerobic curing accelerator contains a hydroquinone compound and benzoquinone represented by the following formula (1).
• X1 to X4 each represent a hydrogen atom or one substituent, and at least one of X1 to X4 is a substituent.
• the number and positions of the substituents can be appropriately determined within the range in which the effects of the embodiments of the present invention can be obtained.
• the number of substituents may be any one to four.
• the position of the substituent may be any of the 2, 3, 5 and 6 positions on the benzene ring in formula (1).
• the substituents may be one or more, all of which may be the same, or may be partially or wholly different.
• substituents include alkyl groups, ester groups and hydroxyl groups.
• the alkyl group may be linear or have a branched structure.
• the number of carbon atoms in the alkyl group may be, for example, 1-10.
• hydroquinone compounds include methylhydroquinone, dimethylhydroquinone, methoxyhydroquinone, 2-t-butylhydroquinone and 2,5-di-t-butylhydroquinone.
• the positional relationship of the two oxygen atoms in the six-membered ring of carbon atoms may be ortho, meta, or para.
• the positional relationship (para) between two hydroxyl groups in the hydroquinone-based compound and the positional relationship between two oxygen atoms in benzoquinone may be the same or different.
• the anaerobic curing accelerator may be composed only of a hydroquinone compound and benzoquinone, or may further contain other components than the hydroquinone compound and benzoquinone.
• the content of the anaerobic curing accelerator in the anaerobic adhesive composition is 0.05 mass with respect to 100 mass parts of the (meth)acrylic monomer from the viewpoint of further enhancing the curability of the anaerobic adhesive composition. It is preferably 0.1 part by mass or more, more preferably 0.1 part by mass or more. From the viewpoint of further enhancing the storage stability of the anaerobic adhesive composition, the amount is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
• the content Ch of the hydroquinone compound in the anaerobic adhesive composition is 0.1 mass with respect to 100 parts by mass of the (meth)acrylic monomer from the viewpoint of expressing the curing acceleration effect of the anaerobic adhesive composition. It is preferably at least 1 part by mass, more preferably at least 0.2 part by mass, even more preferably at least 1 part by mass, and even more preferably at least 2 parts by mass.
• the content Ch of the hydroquinone compound is preferably 5 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic monomer from the viewpoint of sufficiently maintaining and developing the adhesiveness of the anaerobic adhesive composition. , 4 parts by mass or less.
• the content of benzoquinone Cb in the anaerobic adhesive composition is 0.01 mass with respect to 100 mass parts of the (meth)acrylic monomer from the viewpoint of expressing the curing acceleration effect of the anaerobic adhesive composition. parts by mass or more, and more preferably 0.03 parts by mass or more.
• the content of benzoquinone Cb in the anaerobic adhesive composition is 1.00 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic monomer from the viewpoint of promoting the curing of the anaerobic adhesive composition. is preferably 0.10 parts by mass or less, and more preferably 0.08 parts by mass or less.
• the anaerobic adhesive composition of the embodiment of the present invention may further contain a thickening agent.
• a thickener is a component for improving workability by increasing the viscosity of the anaerobic adhesive composition.
• thickeners include acrylic resins, acrylonitrile-butadiene-styrene copolymers (ABS resins) and methyl methacrylate-butadiene-styrene copolymers (MBS resins).
• the content of the thickening agent in the anaerobic adhesive composition can be appropriately determined within a range in which the effect of improving workability is obtained. It may be 40 parts by weight, or it may be 10 to 30 parts by weight.
• the anaerobic adhesive composition of embodiments of the present invention can be prepared by mixing the various ingredients described above.
• the anaerobic adhesive composition of the embodiment of the present invention may be in the form of one liquid in which all of the above various components are mixed, or may contain a part of the above various components and It may be in the form of two or more liquids containing components.
• the anaerobic adhesive composition of the embodiment of the present invention can be used as an adhesive for metal adherends, and is used for preventing loosening of nuts, fixing bearings and shafts, and the like.
• the hydroquinone compound and benzoquinone are components for enhancing the storage stability of the anaerobic adhesive composition, i.e. components that suppress radical polymerization of (meth)acrylic monomers, known as
• a hydroquinone compound together with benzoquinone a component that accelerates the curing of the anaerobic adhesive composition, that is, a radical of a (meth)acrylic monomer It has been found to function as a component that promotes polymerization.
• hydroquinone compounds and benzoquinone are known as materials for anaerobic adhesive compositions. Since these combinations exhibit new functions, it becomes possible to construct an anaerobic adhesive composition with enhanced curing acceleration using fewer kinds of materials.
• anaerobic material adhesive composition whose curing is accelerated is simply constituted, it becomes possible to blend further functional materials, and a multifunctional and high-performance anaerobic material adhesive composition. Development and its spread are expected.
• an anaerobic adhesive composition having curing acceleration properties can be configured with a simpler composition, and saccharin, which is a conventionally known anaerobic curing accelerator, contains a sulfur component.
• saccharin which is a conventionally known anaerobic curing accelerator
• the present invention does not require an anaerobic curing accelerator containing a sulfur component, it is expected that the production of an anaerobic adhesive composition will reduce the burden on the environment.
• embodiments of the present invention are expected to contribute to conservation of land and sea abundance in the Sustainable Development Goals (SDGs).
• the anaerobic adhesive composition in the embodiment of the present invention contains a (meth)acrylic monomer, an organic peroxide and an anaerobic curing accelerator,
• the agent includes a hydroquinone compound represented by formula (1) and benzoquinone.
• the hydroquinone-based compound and benzoquinone accelerate curing of the anaerobic adhesive composition in an anaerobic environment.
• embodiments of the present invention provide anaerobic adhesive compositions containing new components that function as anaerobic accelerators.
• the content of the hydroquinone compound may be 0.1 to 5 parts by mass with respect to 100 parts by mass of the (meth)acrylic monomer.
• the content may be 0.01 to 1.00 parts by mass. This configuration is more effective from the viewpoint of exhibiting the curing acceleration effect of the anaerobic adhesive composition.
• the content of the hydroquinone compound may be 1 to 4 parts by mass with respect to 100 parts by mass of the (meth)acrylic monomer.
• the content may be 0.01 to 1.00 parts by mass. This configuration is much more effective from the viewpoint of exhibiting the curing acceleration effect of the anaerobic adhesive composition.
• anaerobic adhesive composition in the embodiment of the present invention may further contain a thickener. This configuration is much more effective from the viewpoint of enhancing the workability and operability of the anaerobic adhesive composition.
• Example 1 Materials shown in Table 1 below were mixed in amounts (parts by mass) shown in Table 1 in a mixer. Anaerobic adhesive compositions 1 and 2 were thus obtained.
• Method 50 mg of an anaerobic adhesive composition is applied to a 25 mm wide ⁇ 12 mm long portion of one test piece of a cold-rolled steel plate (SPCC-SD) of 25 mm wide ⁇ 100 mm long ⁇ 1.0 mm thick.
• SPCC-SD cold-rolled steel plate
• the adhesive composition coated surface of one test piece is matched with another test piece, and both test pieces are fixed with a clip. Then, it is left in an environment of 23° C. ⁇ 50% RH for 24 hours.
• each test piece was pulled at a peel rate of 2.5 mm/min in a 23°C environment, and the shear strength (N/mm2) at that time was measured. In the case of multiple measurements, the average value was taken as the shear strength of the anaerobic adhesive composition. Then, it was determined that it was practically desirable that the shear strength after 24 hours was 1.00 N / mm or more, and the obtained value of the shear strength was judged according to the following criteria, and the adhesiveness of the anaerobic adhesive composition evaluated.
• anaerobic adhesive composition C1 containing neither hydroquinone compound nor benzoquinone did not cure in an anaerobic environment, or only slightly cured.
• the present invention can be suitably used for adhesion at portions where adherends are in close contact with each other.

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

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• 2022
  • 2022-08-05 CN CN202280054760.3A patent/CN117795026A/zh active Pending
  • 2022-08-05 EP EP22855850.8A patent/EP4386059A4/en active Pending
  • 2022-08-05 JP JP2023541429A patent/JPWO2023017788A1/ja active Pending
  • 2022-08-05 WO PCT/JP2022/030055 patent/WO2023017788A1/ja active Application Filing
• 2023
  • 2023-08-05 US US18/681,290 patent/US20240327686A1/en active Pending

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