Classifications

• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C09J11/08—Macromolecular additives
• • 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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

• (meth)acrylate monomers having one or more (meth)acryloyl groups include, for example, aliphatic (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, neopentyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate.
• aliphatic (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (me
• the content of the radical polymerizable compound (A) is less than 50% by mass based on the total amount of the radical polymerizable adhesive being 100% by mass, the normal adhesiveness (normal tensile shear adhesive strength), hot adhesiveness (hot tensile adhesive strength), hot tensile shear adhesive strength retention rate R a , heat aging resistance (heat aging tensile adhesive strength), heat aging tensile shear adhesive strength retention rate R b , etc. of the radical polymerizable adhesive may be insufficient, and if it exceeds 99% by mass, the normal adhesiveness, hot adhesiveness, heat aging resistance, curing speed, etc. of the radical polymerizable adhesive may be insufficient.
• the organic peroxide (B), which is a component of the radical polymerizable adhesive of the present invention, is used to impart curing properties, for example, anaerobic curing properties and/or heat curing properties, to the radical polymerizable adhesive.
• organic peroxide (B) examples include one or more compounds selected from the group consisting of hydroperoxide compounds such as cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, methyl ethyl ketone peroxide, cyclohexane peroxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, and others, as well as ketone peroxide compounds, diallyl peroxide compounds, peroxy ester compounds, etc.
• hydroperoxide compounds are preferably used.
• an organic peroxide having a one-hour half-life temperature in the range of 80° C. or more, preferably 100° C. or more, and 300° C. or less, preferably 200° C. or less.
• the one-hour half-life temperature is a value measured by thermal decomposition under the condition of an organic peroxide concentration in benzene of 0.1 mol/L.
• Examples of organic peroxides having a one-hour half-life temperature in the range of 80° C. to 300° C. include hydroperoxides.
• hydroperoxides include one or more selected from the group consisting of p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like.
• the content of the (B) organic peroxide in the radical polymerizable adhesive is not particularly limited. It can be, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass or less, relative to 100 parts by mass of the (A) radical polymerizable compound.
• the blending amount of the (B) organic peroxide in the radical polymerizable adhesive can be made more excellent.
• the (C) phosphate compound having a radical polymerizable group which is a component of the radical polymerizable adhesive of the present invention, is a compound represented by the following formula (2) or (3): -O-P(O)(OH)-O-...(2) -OP(O)(OH) 2 ...(3)
• the compound is at least one phosphoric acid ester compound having a group represented by the following formula: Examples of the radical polymerizable functional group include ethylenically unsaturated bonds.
• Examples of the ethylenically unsaturated bond include (meth)acryloyl groups, vinyl groups, allyl groups, (meth)acrylamide groups, styryl groups, alkenyl groups, alkenylene groups, and maleimide groups, among which (meth)acryloyl groups are preferred.
• the number of radical polymerizable groups possessed by the phosphoric acid ester compound having a radical polymerizable group (C) is not particularly limited. It is 1 or more, and can be 3 or less, preferably 2 or less, in view of reactivity and availability.
• the phosphoric acid ester compound having a radical polymerizable group (C) in combination with the radical polymerizable compound (A) and the organic peroxide (B), it is possible to obtain a radical polymerizable adhesive that exhibits excellent adhesive strength (normal tensile shear adhesive strength) to various adherends, such as metal plates and plastics, especially steel plates, and has a remarkable effect.
• the phosphate ester compound having a radical polymerizable group is not particularly limited, but examples thereof include one or more selected from the group consisting of 2-hydroxymethyl (meth)acrylate acid phosphate, 2-hydroxyethyl (meth)acrylate acid phosphate, 2-hydroxypropyl (meth)acrylate acid phosphate, bis(meth)acryloyloxy acid phosphate, bis(2-(meth)acryloyloxyethyl acid) phosphate, di-(2-(meth)acryloyloxy)hydrogen phosphate, ethylene oxide modified phosphate di(meth)acrylate, ethylene oxide modified phosphate tri(meth)acrylate, caprolactone modified ethylene oxide modified phosphate di(meth)acrylate, dipentaerythritol penta(meth)acryloyloxydihydrogen phosphate, etc.
• the phosphate ester compound having a radical polymerizable group may be synthesized or a commercially available product may be used.
• commercially available products include one or more selected from the group consisting of Light Ester P-A, P-1M, P-2M (all manufactured by Kyoeisha Chemical Co., Ltd.), Kayamar PM-1 (manufactured by Nippon Kayaku Co., Ltd.), JPA-514 (manufactured by Johoku Chemical Industry Co., Ltd.), etc.
• the content of the phosphoric acid ester compound having a radical polymerizable group (C) in the radical polymerizable adhesive is not particularly limited. From the viewpoint of normal adhesion (normal tensile shear adhesive strength), hot adhesion (hot tensile adhesive strength), hot tensile shear adhesive strength retention rate R a , heat aging resistance (heat aging tensile adhesive strength), heat aging tensile shear adhesive strength retention rate R b , and curing speed, the content of the phosphoric acid ester compound having a radical polymerizable group (C) is, for example, 0.05 parts by mass or more, preferably 0.06 parts by mass or more, more preferably 0.07 parts by mass or more, and can be, for example, less than 1.0 parts by mass, preferably 0.8 parts by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the radical polymerizable compound (A).
• the curing speed may be insufficient.
• the content is less than 0.05 part by mass, the normal adhesion (normal tensile shear bond strength), hot adhesion (hot tensile bond strength), hot tensile shear bond strength retention R a , heat aging resistance (heat aging tensile bond strength), heat aging tensile shear bond strength retention R b , etc. of the radical polymerizable adhesive may be insufficient.
• the non-radical polymerizable polymer (D) having a molecular weight of 1,000 or more which is a component of the radical polymerizable adhesive of the present invention, is a polymer having a weight average molecular weight of 1,000 or more and having no radical polymerizable group in the molecule.
• the radical polymerizable functional group may be, for example, an ethylenically unsaturated bond.
• the ethylenically unsaturated bond may be, for example, a (meth)acryloyl group, a vinyl group, an allyl group, a (meth)acrylamide group, a styryl group, an alkenyl group, an alkenylene group, a maleimide group, etc.
• the weight average molecular weight of the non-radical polymerizable polymer having a molecular weight of 1,000 or more is not particularly limited as long as it is 1,000 or more.
• it is 3,000 or more, preferably 5,000 or more, more preferably 10,000 or more, and for example, 500,000 or less, preferably 300,000 or less, more preferably 200,000 or less.
• the weight average molecular weight for example, the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) can be used.
• the glass transition temperature (Tg) of the non-radical polymerizable polymer having a molecular weight of 1,000 or more is not particularly limited. For example, it is -50°C or higher, preferably -20°C or higher, more preferably 10°C or higher, and for example, it is 200°C or lower, preferably 150°C or lower, more preferably 120°C or lower.
• the glass transition temperature (Tg) can be determined from the weight loss of the TG curve obtained by performing simultaneous differential thermal analysis (TG/DTA) at 600°C under conditions of a nitrogen atmosphere, a heating rate of 5°C/min, and a tensile mode (100 mN) using a thermal analyzer.
• non-radical polymerizable polymers having a molecular weight of 1,000 or more include one or more selected from the group consisting of (meth)acrylic resins, polyolefin resins, polystyrene resins, epoxy resins, rubber/elastomers, polyvinyl alcohol resins, polyvinyl ester resins, diene resins, ABS resins, AS resins, styrene/butadiene resins, halogenated vinyl resins, cyclic polyolefin resins, polyester resins, polyether resins, phenoxy resins, urethane resins, polyamide resins, polycarbonate resins, polyimide resins, polysiloxane resins, phenolic resins, cellulose resins, rosin resins, and modified resins of these resins.
• the radically polymerizable adhesive of the present invention preferably has a tensile shear bond strength (normal tensile shear bond strength) of 2.50 N/ mm2 or more when bonded at 23°C. It is preferably 2.75 N/ mm2 or more, more preferably 3.00 N/ mm2 or more, and even more preferably 3.25 N/mm2 or more .
• the upper limit of the tensile shear bond strength (normal tensile shear bond strength) when bonded at 23°C is not particularly limited, but is, for example, 9.00 N/ mm2 or less.
• the tensile shear adhesive strength (normal tensile shear adhesive strength) when bonded at 23° C. can be confirmed by the method described in “Normal tensile shear adhesive strength” in the Examples.
• the viscosity of the radically polymerizable adhesive of the present invention is not particularly limited. From the viewpoint of ease of handling, prevention of overflow during adhesion, etc., the viscosity is, for example, 0.01 Pa ⁇ s or more, preferably 0.05 Pa ⁇ s or more, more preferably 0.5 Pa ⁇ s or more, and can be, for example, 50 Pa ⁇ s or less, preferably 30 Pa ⁇ s or less, more preferably 15 Pa ⁇ s or less.
• the viscosity can be adjusted by a method known in the adhesive field, such as blending a viscosity modifier (thixotropic agent).
• the viscosity can be obtained, for example, by putting 100 g of the radical polymerizable adhesive into a bottle, discharging it into a measuring cup, and measuring it using a Brookfield viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25° C. and a rotation speed of 60 rpm.
• a Brookfield viscometer manufactured by Toki Sangyo Co., Ltd.
• the method for producing the radical polymerizable adhesive of the present invention is not particularly limited.
• the adhesive can be produced by adding predetermined amounts of at least (A) the radical polymerizable compound, (B) the organic peroxide, and (C) the phosphoric acid ester compound having a radical polymerizable group to a mixing vessel in any order and mixing them.
• a mixing device such as a mixer (such as a rotation/revolution mixer or a planetary mixer), a tumbler, a stirrer, an agitator, a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, a shaker, a V-type blender, or a Nauta mixer can be used, and it is preferable to use a mixer.
• the mixing conditions are not particularly limited.
• the temperature conditions are, for example, 0° C. or higher, preferably 10° C. or higher, and, for example, 100° C. or lower, preferably 70° C. or lower.
• the mixing time is, for example, 1 minute or longer, preferably 5 minutes or longer, and, for example, 10 hours or shorter, preferably 5 hours or shorter.
• the radical polymerizable adhesive of the present invention can be used as an anaerobic adhesive.
• the radical polymerizable adhesive is preferably an anaerobic adhesive, particularly an anaerobic adhesive for metals.
• the radically polymerizable adhesive of the present invention can be used in a variety of fields, such as for various electric and electronic parts, automobiles, machines, buildings, and civil engineering.
• the radical polymerizable adhesive of the present invention can be used to bond various adherends, and can rapidly cure and bond at 25°C (room temperature).
• Adherends include one or more of various metals such as iron, aluminum, magnesium, stainless steel, titanium, and copper, resins, glass, ceramics, paper, cloth, and fiber.
• the radical polymerizable adhesive of the present invention has excellent adhesion to metals and is preferably used for metals, and in particular, due to its curing property, it may be applied to molded products in which two or more metal plates are bonded together.
• metal plates include one or more selected from steel plates (various iron steel plates such as cold-rolled steel plates (SPCC, SPCC-SD), painted steel plates, etc.), aluminum plates, stainless steel plates, magnesium plates, and copper plates.
• the thickness of the metal plate is not particularly limited and can be appropriately determined depending on the application, etc. For example, it is 0.01 mm or more, preferably 0.1 mm or more, and for example, it is 5 mm or less, preferably 3 mm or less, and more preferably 1 mm or less.
• the primer applied to the metal preferably contains a transition metal compound, particularly a copper compound, as a radically polymerizable adhesion promoter.
• the primer may also contain a liquid medium, a rust inhibitor, a preservative, etc.
• the copper compound may be one or more selected from the group consisting of copper salts of carboxylic acids such as copper neodecanoate, copper 2-ethylhexanoate, copper naphthenate, copper octenate, copper hexanoate, copper propionate, and copper 2,4-pentanedione (copper acetylacetonate); copper complexes such as copper ethylenediamine and copper propylenediamine; and the like.
• carboxylic acids such as copper neodecanoate, copper 2-ethylhexanoate, copper naphthenate, copper octenate, copper hexanoate, copper propionate, and copper 2,4-pentanedione (copper acetylacetonate)
• copper complexes such as copper ethylenediamine and copper propylenediamine; and the like.
• the liquid medium may include one or more organic solvents and/or water.
• the organic solvent is not particularly limited.
• the solvent include at least one selected from the group consisting of aliphatic hydrocarbon solvents having 5 to 40 carbon atoms (hexane, heptone, paraffin, etc.); alicyclic hydrocarbon solvents having 5 to 20 carbon atoms; aromatic hydrocarbon solvents having 6 to 20 carbon atoms (benzene, toluene, xylene, ethylbenzene, indene, etc.); alcohol solvents having 1 to 10 carbon atoms (methanol, ethanol, propanol, isopropanol, hexanol, etc.); ketone solvents having 3 to 20 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.); ether solvents having 2 to 20 carbon atoms (tetrahydrofuran, diethyl ether,
• the composition of the primer is not particularly limited.
• the copper compound is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and for example, 15.0% by mass or less, preferably 10.0% by mass or less, more preferably 8.0% by mass or less, when the total amount of the primer is taken as 100% by mass.
• the oils in the liquid medium are, for example, 20.0% by mass or more, preferably 25.0% by mass or more, more preferably 30.0% by mass or more, and for example, 80.0% by mass or less, preferably 70.0% by mass or less, more preferably 60.0% by mass or less, when the total amount of the primer is taken as 100% by mass.
• the normal tensile shear adhesive strength is the tensile shear adhesive strength when bonded at 23° C., and can be obtained as follows. Two cold-rolled steel sheets were prepared for testing. One of the sheets was spray-coated with a primer and left to dry at 25°C for 3 hours. The other sheet was coated with 0.03 ml of a radically polymerizable adhesive with a spatula, and immediately after coating of the radically polymerizable adhesive, the primer-coated surface and the radically polymerizable adhesive-coated surface were bonded together so that the bonding area was 25 mm wide x 12.5 mm long. The two test pieces were then clamped for 200 seconds and removed to prepare test pieces.
• the prepared test pieces were aged in an environment of 23° C. for 24 hours and then pulled at 23° C. with a universal tensile tester at a pulling speed of 0.5 mm/min to obtain normal tensile shear adhesive strength (N/mm 2 ) according to JIS K 6850 (1999).
• the hot tensile shear adhesive strength is a hot tensile shear adhesive strength at 150° C., and can be obtained as follows. Two cold-rolled steel sheets were prepared for testing. One of the sheets was spray-coated with a primer and left to dry at 25°C for 3 hours. The other sheet was coated with 0.03 ml of a radically polymerizable adhesive with a spatula, and immediately after coating of the radically polymerizable adhesive, the primer-coated surface and the radically polymerizable adhesive-coated surface were bonded together so that the bonding area was 25 mm wide x 12.5 mm long.
• test pieces were then clamped for 200 seconds to perform anaerobically bonding, and then removed to prepare a test piece.
• the prepared test pieces were aged in an environment of 23° C. for 24 hours, and then pulled at a hot temperature of 150° C. at a tensile speed of 0.5 mm/min using a universal tensile tester to obtain the hot tensile shear adhesive strength (N/mm 2 ) according to JIS K 6850 (1999).
• the heat aging tensile shear adhesive strength is the tensile shear adhesive strength after heating at 200° C. for 2 hours and cooling to 23° C., and can be obtained as follows. Two cold-rolled steel sheets were prepared for testing. One of the sheets was spray-coated with a primer and left to dry at 25°C for 3 hours. The other sheet was coated with 0.03 ml of a radically polymerizable adhesive with a spatula, and immediately after coating of the radically polymerizable adhesive, the primer-coated surface and the radically polymerizable adhesive-coated surface were bonded together so that the bonding area was 25 mm wide x 12.5 mm long.
• the two test pieces were then clamped for 200 seconds to perform anaerobically bonding, and then removed to prepare a test piece.
• the prepared test pieces were aged in an environment of 23°C for 24 hours, then heated at 200°C for 2 hours, left to cool to 23°C after heating, and then pulled at a tensile speed of 0.5 mm/min using a universal tensile tester to obtain the heat aging tensile shear adhesive strength (tensile shear adhesive strength after heating at 200°C for 2 hours and cooling to 23°C) (N/ mm2 ) according to JIS K 6850 (1999).
• the hot tensile shear strength retention rate R a is calculated by the formula (i):
• A is the tensile shear adhesive strength (normal tensile shear adhesive strength) (N/mm 2 ) when bonded at 23° C.
• B is the hot tensile shear adhesive strength (hot tensile shear adhesive strength) (N/mm 2 ) at 150° C.
• the heat aging tensile shear strength retention rate Rb is calculated by the formula (ii):
• A is the tensile shear adhesive strength (normal tensile shear adhesive strength) (N/mm 2 ) when bonded at 23°C
• C is the tensile shear adhesive strength (heat aging tensile shear adhesive strength) (N/mm 2 ) after heating at 200°C for 2 hours and cooling to 23°C.
• Examples A1 to A6, Comparative Example A1 ⁇ Preparation of radically polymerizable adhesive>
• Each of the components shown in Table 1 was taken in the amount (parts by mass) shown in Table 1 and mixed in a glass container to prepare a radically polymerizable adhesive.
• the normal tensile shear adhesive strength tensile shear adhesive strength when bonded at 23°C
• hot tensile shear adhesive strength hot tensile shear adhesive strength at 150°C
• the normal tensile shear adhesive strength (tensile shear adhesive strength when bonded at 23° C.) and the hot tensile shear strength retention rate R a are also shown in Table 1.
• Examples B1 to B6, Comparative Example B1] ⁇ Preparation of radically polymerizable adhesive>
• Each of the components shown in Table 2 was taken in the amount (parts by mass) shown in Table 2 and mixed in a glass container to prepare a radically polymerizable adhesive.
• the normal tensile shear adhesive strength tensile shear adhesive strength when bonded at 23°C
• the heat aging tensile shear adhesive strength tensile shear adhesive strength after heating at 200°C for 2 hours and cooling to 23°C
• the normal tensile shear adhesive strength (tensile shear adhesive strength when bonded at 23° C.) and the heat aging tensile shear adhesive strength retention rate Rb are also shown in Table 2.

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• Chemical Kinetics & Catalysis (AREA)
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• Macromonomer-Based Addition Polymer (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2024
  • 2024-12-24 JP JP2025543244A patent/JP7776047B2/ja active Active
  • 2024-12-24 WO PCT/JP2024/045737 patent/WO2025142949A1/ja active Pending
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