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
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
  • C09J109/02—Copolymers with acrylonitrile
• • 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
  • 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
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
  • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
• • 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
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Definitions

• the present invention relates to a composition, an article, and a motor.
• Adhesives are used in motors to secure magnets. Adhesives are used, for example, to bond the rotor and magnet, or the stator and magnet of the motor.
• Patent Document 1 describes a radical curable resin composition that contains (A) component: a vinyl polymer containing a terminal (meth)acrylic group; (B) component: a radical polymerizable monomer selected from the group consisting of isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, acryloylmorpholine, dimethylacrylamide, and diethylacrylamide; (C) component: a (meth)acrylate or (meth)acrylic acid having a phosphate group; and (D) component: a radical initiator, with the aim of providing a radical curable resin composition that has excellent adhesive strength with metal members such as magnets and that produces a cured product that does not crack or peel off even after a thermal cycle test required for vehicle-mounted members.
• the composition is characterized by containing 5 to 140 parts by mass of (B) component per 100 parts by mass of (A) component.
• Patent Document 2 describes a composition containing the following (A) to (D), which is intended for use as an adhesive in the manufacture of automobiles.
• A a urethane (meth)acrylate having a number average molecular weight of 5,000 or more, in an amount of 40 to 75 parts by mass per 100 parts by mass of the total of (A) and (B);
• B-1) a (meth)acrylate having no urethane bond, and
• B-2) a (meth)acrylic compound containing 15 to 25 parts by mass of (meth)acrylic acid per 100 parts by mass of the total of (A) and (B);
• C a polymerization initiator; and
• D a reducing agent.
• Patent Document 3 describes a two-component adhesive consisting of a first part containing a free radical initiator and a second part containing a reducing agent, with the aim of providing a two-component adhesive having high heat resistance and moisture resistance that can be used as a structural adhesive.
• This two-component adhesive contains a first monomer which is methyl methacrylate and a second monomer selected from the group consisting of methacrylic acid, polyfunctional (meth)acrylic acid adducts of aromatic polyols or derivatives thereof, and combinations thereof.
• the overlap shear strength of the cured product of this two-component adhesive is 20 MPa or more at 25°C and 7 MPa or more at 120°C, the adhesive strength in a T-peel test at 25°C is 2 kN/m or more, and the glass transition temperature is 130°C or more.
• adhesives used in motors and other devices are required to have thermal fatigue resistance that can withstand the tensile force caused by centrifugal forces applied in high-temperature environments in order to accommodate the higher temperatures required for use in environments where motors are becoming smaller and more powerful.
• the present invention was made in consideration of the above circumstances, and provides a composition with improved thermal fatigue resistance, as well as an article and a motor using the composition.
• the present inventors have conducted extensive research to achieve the above object. As a result, they have discovered that the thermal fatigue resistance of a composition containing a polymerizable monomer including a monofunctional (meth)acrylate and a highly polar monomer, and an elastomer, can be improved by setting the glass transition temperature of the cured product of the composition within a specific range, and have thus completed the present invention.
• the present invention provides the following compositions, articles, and motors.
• a composition comprising a polymerizable monomer (A) and an elastomer (B), the polymerizable monomer (A) comprises a monofunctional (meth)acrylate (A1) and a highly polar monomer (A2);
• the composition is cured at 23° C. for 24 hours, and the cured product has a glass transition temperature of 180° C. or higher, as determined by dynamic viscoelasticity measurement.
• composition according to [3] above, wherein the tricyclic monofunctional (meth)acrylate comprises one or more selected from the group consisting of monofunctional (meth)acrylates having a structure including a dicyclopentane skeleton and a ring connected to the dicyclopentane skeleton, and monofunctional (meth)acrylates having a dicyclopentadiene skeleton.
• the content of the monofunctional (meth)acrylate (A1) is 1 part by mass or more and 50 parts by mass or less when the total content of the polymerizable monomer (A) and the elastomer (B) is 100 parts by mass.
• polyfunctional (meth)acrylate (A3) includes one or more selected from the group consisting of polyfunctional (meth)acrylates having an alicyclic structure, polyfunctional (meth)acrylates having an aromatic ring structure, and polyfunctional (meth)acrylates having an aliphatic chain structure.
• polyfunctional (meth)acrylate (A3) contains 2 to 6 (meth)acryloyl groups.
• the elastomer (B) contains one or more selected from the group consisting of (meth)acrylonitrile-butadiene rubber, methyl(meth)acrylate-butadiene-styrene rubber, and methyl(meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber.
• the composition according to [15] which is used for fixing between a magnet and a rotor or between a magnet and a stator in the motor.
• An article comprising a cured product of the composition according to any one of [1] to [16] above.
• a motor comprising a cured product of the composition according to any one of [1] to [16] above.
• the present invention provides a composition with improved thermal fatigue resistance, as well as an article and a motor using the composition.
• the expression "X to Y" in the description of a numerical range means from X to Y.
• “1 to 5% by mass” means "1% by mass to 5% by mass.”
• the content of each component preferably represents the content relative to the total content of the first agent and the second agent.
• groups atomic groups
• the notation includes both groups having no substituents and groups having a substituent.
• an "alkyl group” includes not only an alkyl group having no substituents (an unsubstituted alkyl group) but also an alkyl group having a substituent (a substituted alkyl group).
• the term "(meth)acrylic” refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate.”
• the term "organic group” refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound.
• a “monovalent organic group” refers to an atomic group obtained by removing one hydrogen atom from any organic compound.
• the adhesive composition of the present embodiment is an adhesive composition comprising a polymerizable monomer (A) and an elastomer (B), wherein the polymerizable monomer (A) comprises a monofunctional (meth)acrylate (A1) and a highly polar monomer (A2), and the composition is cured at 23°C for 24 hours, and the cured product has a glass transition temperature of 180°C or higher, as determined by dynamic viscoelasticity measurement.
• the glass transition temperature of the cured product of the adhesive composition of the present embodiment is an effective design guideline for improving thermal fatigue resistance.
• the inventors have found that by controlling the glass transition temperature of the cured product within a specific range, it is possible to obtain an adhesive composition with improved thermal fatigue resistance, as well as an article and a motor using the adhesive composition.
• the adhesive composition of the present embodiment can provide articles and motors with improved thermal fatigue resistance. Furthermore, the present inventors have found that the adhesive composition of the present embodiment can achieve both thermal fatigue resistance and heat cycle resistance, i.e., the adhesive composition of the present embodiment can realize an article and a motor with an improved performance balance between thermal fatigue resistance and heat cycle resistance.
• the thermal fatigue resistance property means the repeated fatigue property under high temperature
• the heat cycle resistance property means the adhesive strength after heat cycle treatment.
• the glass transition temperature of the cured product is preferably 183°C or higher, more preferably 185°C or higher, even more preferably 188°C or higher, even more preferably 190°C or higher, even more preferably 195°C or higher, even more preferably 198°C or higher, and is preferably 350°C or lower, more preferably 300°C or lower, even more preferably 250°C or lower, even more preferably 230°C or lower, even more preferably 220°C or lower, and even more preferably 210°C or lower.
• the glass transition temperature of the cured product of the adhesive composition of the present embodiment can be adjusted, for example, by adjusting the type and content ratio of each component contained in the adhesive composition of the present embodiment, the order and method of mixing each component, etc.
• the adhesive composition of the present embodiment contains a polymerizable monomer (A).
• the polymerizable monomer (A) does not contain an elastomer (B) described below.
• the polymerizable monomer (A) includes a monofunctional (meth)acrylate (A1) and a highly polar monomer (A2).
• the monofunctional (meth)acrylate (A1) refers to a compound having one (meth)acryloyl group, provided that the monofunctional (meth)acrylate (A1) does not include those that fall under the category of the highly polar monomer (A2).
• the monofunctional (meth)acrylate (A1) preferably contains a monomer represented by the following general formula (I).
• CH 2 CHR 1 -COO-R 2 (I)
• R1 is a hydrogen atom or a methyl group
• R2 is a group containing a cyclic hydrocarbon skeleton, preferably a group containing a polycyclic cyclic hydrocarbon skeleton.
• the cyclic hydrocarbon skeleton contained in R2 is preferably an alicyclic skeleton not containing an aromatic ring.
• the monofunctional (meth)acrylate (A1) preferably contains a tricyclic monofunctional (meth)acrylate in which the three rings are alicyclic (hereinafter also referred to as "tricyclic monofunctional (meth)acrylate”).
• tricyclic ring refers to three connected rings.
• trimic monofunctional (meth)acrylate in this embodiment refers to a monofunctional (meth)acrylate having an alicyclic hydrocarbon group containing three connected rings.
• the alicyclic hydrocarbon group is preferably an unsubstituted saturated hydrocarbon group.
• the tricyclic monofunctional (meth)acrylate preferably includes one or more selected from the group consisting of monofunctional (meth)acrylates having a structure including a dicyclopentane skeleton and a ring connected to the dicyclopentane skeleton, and monofunctional (meth)acrylates having a dicyclopentadiene skeleton, more preferably includes one or more selected from the group consisting of dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentenyl (meth)acrylate, and further preferably includes dicyclopentanyl (meth)acrylate.
• An example of the dicyclopentanyl (meth)acrylate is FA-513M manufactured by Hitachi Chemical Co., Ltd.
• the content of the monofunctional (meth)acrylate (A1) in the adhesive composition of this embodiment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 18 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less.
• the ratio of tricyclic monofunctional (meth)acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 75% by mass or more, even more preferably 80% by mass or more, even more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 100% by mass or less.
• the highly polar monomer (A2) is, for example, a polymerizable monomer having a polar functional group and a carbon-carbon double bond.
• the highly polar monomer (A2) may be a monofunctional monomer (a monomer having one carbon-carbon double bond) or a polyfunctional monomer (a monomer having multiple carbon-carbon double bonds), but is preferably a monofunctional monomer.
• the polar functional group possessed by the highly polar monomer (A2) preferably contains one or more types selected from the group consisting of a carboxy group, a hydroxy group, and a phosphate group, more preferably contains one or more types selected from the group consisting of a carboxy group and a phosphate group, and even more preferably contains a carboxy group.
• the highly polar monomer (A2) preferably contains one or more monomers selected from the group consisting of (meth)acrylic acid, fumaric acid, maleic acid, fumaric anhydride, maleic anhydride, monomers having a phosphoric acid group and a (meth)acryloyl group, and hydroxyalkyl (meth)acrylates, more preferably contains one or more monomers selected from the group consisting of (meth)acrylic acid and monomers having a phosphoric acid group and a (meth)acryloyl group, even more preferably contains (meth)acrylic acid, and even more preferably contains methacrylic acid.
• the content of the highly polar monomer (A2) in the adhesive composition of this embodiment when the total content of the polymerizable monomer (A) and the elastomer (B) is taken as 100 parts by mass, is preferably 15 parts by mass or more, more preferably 18 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 22 parts by mass or more, and is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 28 parts by mass or less.
• the polymerizable monomer (A) may further include a polyfunctional (meth)acrylate (A3).
• the polyfunctional (meth)acrylate (A3) refers to a compound having two or more carbon-carbon double bonds such as a (meth)acryloyl group, provided that the polyfunctional (meth)acrylate (A3) does not include those that fall under the category of the highly polar monomer (A2).
• the polyfunctional (meth)acrylate (A3) preferably contains 2 to 6 (meth)acryloyl groups, more preferably contains 2 to 4 (meth)acryloyl groups, even more preferably contains 2 to 3 (meth)acryloyl groups, and still more preferably contains 2 (meth)acryloyl groups.
• the polyfunctional (meth)acrylate (A3) preferably includes one or more selected from the group consisting of polyfunctional (meth)acrylates having an alicyclic structure, polyfunctional (meth)acrylates having an aromatic ring structure, and polyfunctional (meth)acrylates having an aliphatic chain structure.
• Examples of the polyfunctional (meth)acrylate having an alicyclic structure include one or more selected from the group consisting of dicyclopentanyl di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, and dimethylol-cyclohexane di(meth)acrylate.
• polyfunctional (meth)acrylates having an aromatic ring structure include one or more selected from the group consisting of 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloxytetraethoxyphenyl)propane, ethylene oxide-added bisphenol A di(meth)acrylate (EO-modified BPA di(meth)acrylate), ethylene oxide-added bisphenol F di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, and propylene oxide-added bisphenol F di(meth)acrylate.
• EO-modified BPA di(meth)acrylate ethylene oxide-added bisphenol F di(meth)acrylate
• propylene oxide-added bisphenol A di(meth)acrylate propylene oxide-added bisphenol F di(meth)acrylate.
• polyfunctional (meth)acrylates having an aliphatic chain structure examples include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexadiol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and isocyanuric acid ethylene oxide modified di(meth)acrylate.
• the polyfunctional (meth)acrylate (A3) more preferably includes one or more selected from the group consisting of dicyclopentanyl di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and even more preferably includes dicyclopentanyl di(meth)acrylate.
• the content of the polyfunctional (meth)acrylate (A3) in the adhesive composition of this embodiment is, when the total content of the polymerizable monomer (A) and the elastomer (B) is taken as 100 parts by mass, preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 18 parts by mass or less, even more preferably 16 parts by mass or less.
• the content of the polymerizable monomer (A) in the adhesive composition of this embodiment when the total content of the polymerizable monomer (A) and the elastomer (B) is taken as 100 parts by mass, is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, even more preferably 38 parts by mass or more, even more preferably 40 parts by mass or more, and is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 65 parts by mass or less, even more preferably 60 parts by mass or less.
• the adhesive composition of the present embodiment contains an elastomer (B).
• the elastomer (B) preferably has a soft segment unit.
• the soft segment unit preferably contains one or more selected from the group consisting of a diene structure, an ethylene structure, a propylene structure, an isoprene structure, a urethane structure, an ethylene glycol structure, a propylene glycol structure, a silicone structure, and a chloroprene structure, and more preferably contains a diene structure such as a butadiene structure.
• the elastomer (B) may have a hard segment in addition to the soft segment unit.
• the "soft segment” refers to a flexible portion exhibiting rubber elasticity.
• the "hard segment” refers to a molecular restraint portion that serves as a crosslinking point of a crosslinked rubber that prevents plastic deformation.
• the content of the soft segment units in the elastomer (B) is preferably 15% by mass or more and 90% by mass or less, more preferably 25% by mass or more and 85% by mass or less, of the entire elastomer of this embodiment.
• the elastomer (B) preferably contains one or more types selected from the group consisting of (meth)acrylonitrile-butadiene rubber, methyl (meth)acrylate-butadiene-styrene rubber, and methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber, more preferably contains one or two types selected from the group consisting of (meth)acrylonitrile-butadiene rubber and methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber, and even more preferably contains both (meth)acrylonitrile-butadiene rubber and methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber.
• the adhesive composition of this embodiment may contain only one elastomer, or may contain two or more elastomers.
• one or two selected from the group consisting of the above-mentioned methyl (meth)acrylate-butadiene-styrene rubber and methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber may be used in combination with (meth)acrylonitrile-butadiene rubber.
• the ratio of the two elastomers in mass ratio is preferably 0.5:9.5 to 9.5:0.5, more preferably 0.8:9.2 to 9.2:0.8, and even more preferably 1.0:9.0 to 9.0:1.0.
• the content of elastomer (B) in the adhesive composition of this embodiment when the total content of polymerizable monomer (A) and elastomer (B) is taken as 100 parts by mass, is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, even more preferably 40 parts by mass or more, and is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, even more preferably 62 parts by mass or less, even more preferably 60 parts by mass or less.
• the adhesive composition of the present embodiment preferably contains a polymerization initiator (C).
• the polymerization initiator (C) polymerizes the carbon-carbon double bonds of the polymerizable monomer (A), thereby improving the adhesiveness.
• the polymerization initiator (C) preferably contains a thermal radical polymerization initiator.
• the thermal radical polymerization initiator preferably contains an organic peroxide, more preferably contains one or more selected from the group consisting of cumene hydroperoxide, paramenthane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, and tertiary butyl peroxybenzoate, and further preferably contains cumene hydroperoxide.
• the content of the polymerization initiator (C) in the adhesive composition of this embodiment when the total content of the polymerizable monomer (A) and the elastomer (B) is taken as 100 parts by mass, is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, and even more preferably 1.5 parts by mass or more, and is preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less, even more preferably 12.0 parts by mass or less, even more preferably 10.0 parts by mass or less, even more preferably 8.0 parts by mass or less, even more preferably 6.0 parts by mass or less, even more preferably 4.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.
• the adhesive composition of the present embodiment preferably contains a reducing agent (D).
• the adhesive composition of the present embodiment can further improve the curability by using the polymerization initiator (C) and the reducing agent (D) in combination.
• the reducing agent (D) may be any reducing agent that reacts with the polymerization initiator (C) to generate radicals.
• the reducing agent (D) preferably contains one or more selected from the group consisting of tertiary amines, thiourea derivatives, and transition metal salts, and more preferably contains a transition metal salt.
• Examples of the tertiary amine include one or more selected from the group consisting of triethylamine, tripropylamine, tributylamine, and N,N-dimethyl-p-toluidine.
• Examples of the thiourea derivative include one or more selected from the group consisting of 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, ethylenethiourea, acetyl-2-thiourea, benzoylthiourea, N,N-diphenylthiourea, N,N-diethylthiourea, N,N-dibutylthiourea, and tetramethylthiourea.
• transition metal salt examples include one or more selected from the group consisting of cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate, etc. More preferably, the transition metal salt includes vanadyl acetylacetonate.
• the content of the reducing agent (D) in the adhesive composition of this embodiment when the total content of the polymerizable monomer (A) and the elastomer (B) is taken as 100 parts by mass, is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, even more preferably 0.15 parts by mass or more, even more preferably 0.20 parts by mass or more, and is preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less, even more preferably 1.0 parts by mass or less, even more preferably 0.50 parts by mass or less.
• the adhesive composition of the present embodiment may or may not contain other components in addition to those described above.
• the adhesive composition of the present embodiment may contain paraffin.
• paraffin for example, various paraffins can be used to rapidly harden the part in contact with air.
• the paraffin for example, one or more kinds selected from the group consisting of paraffin wax, microcrystalline wax, carnauba wax, beeswax, lanolin, spermaceti, ceresin, candelilla wax, etc. can be mentioned.
• the adhesive composition of the present embodiment may contain only one paraffin, or may contain two or more paraffins.
• the content of paraffin in the adhesive composition of the present embodiment is preferably 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.1 parts by mass or more and 2 parts by mass or less, when the total content of the polymerizable monomer (A) and the elastomer (B) is taken as 100 parts by mass, from the viewpoint of further improving curability.
• the adhesive composition of the present embodiment may contain various stabilizers from the viewpoint of further improving storage stability.
• the stabilizers include (i) phenol-based antioxidants (e.g., 2,2'-methylenebis(4-methyl-6-t-butylphenol) and the like), (ii) quinone-based compounds (e.g., p-benzoquinone, hydroquinone monomethyl ether, and the like), (iii) compounds known as polymerization inhibitors (e.g., amine-based polymerization inhibitors such as phenothiazine, citric acid, and the like), and (iv) stable radical-type compounds having stable radicals.
• phenol-based antioxidants e.g., 2,2'-methylenebis(4-methyl-6-t-butylphenol) and the like
• quinone-based compounds e.g., p-benzoquinone, hydroquinone monomethyl ether, and the like
• polymerization inhibitors e.g., amine
• the content of the stabilizer in the adhesive composition of this embodiment is, from the viewpoint of further improving storage stability while suppressing deterioration in performance as an adhesive composition, preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, even more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, and is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less, even more preferably 1.5 parts by mass or less, and even more preferably 1.0 parts by mass or less, when the total content of the polymerizable monomer (A) and the elastomer (B) is taken as 100 parts by mass.
• the adhesive composition of this embodiment is cured at 23°C for 24 hours to obtain a 1BA type dumbbell test piece described in JIS K 7161-2:2014 Appendix A.
• the breaking elongation measured in accordance with JIS K 7161-2:2014 under conditions of 23°C and a tensile speed of 10 mm/min, is preferably 30% or more, more preferably 35% or more, even more preferably 38% or more, even more preferably 40% or more, even more preferably 45% or more, even more preferably 48% or more, and preferably 100% or less, from the viewpoint of further improving the heat cycle resistance.
• the moderately large breaking elongation of the cured product of the adhesive composition means that the cured product of the adhesive composition effectively relieves stress generated in a heat cycle test, etc.
• the moderately large breaking elongation of the cured product of the adhesive composition effectively relieves stress.
• the breaking elongation of the adhesive composition of this embodiment can be adjusted, for example, by adjusting the type and content ratio of each component contained in the adhesive composition of this embodiment, the order and method of mixing each component, etc.
• the adhesive composition of the present embodiment may be a one-component type or a two-component type (two components filled in separate containers are mixed together immediately before use).
• the polymerization initiator (C) is preferably contained in the first component
• the reducing agent (D) is preferably contained in the second component.
• the adhesive composition of the present embodiment is of a two-part type, it is preferable to adjust the amount of each component in the first and second parts so that the adhesive composition after mixing the first and second parts contains each component in the preferred content range described above.
• various properties of the adhesive composition described in this specification relate to the adhesive composition after mixing the first and second parts.
• ⁇ Method for producing adhesive composition> In producing the adhesive composition of the present embodiment, it is preferable to appropriately adjust the order of mixing the components, the mixing method, etc., rather than simply mixing the above-mentioned components. In the production of the adhesive composition of this embodiment, it is particularly preferable that the polymerizable monomer (A) and the elastomer (B) are mixed sufficiently. For this reason, as shown in the examples below, it is preferable to (i) first mix at least a part of the polymerizable monomer (A) and at least a part of the elastomer (B) sufficiently uniformly at 50 to 80° C. to obtain a mixture, and (ii) then add other components to the mixture and stir it.
• the polymerizable monomer (A) and the elastomer (B) are mixed sufficiently uniformly.
• the adhesive composition produced in this way tends to easily satisfy, for example, the properties of the adhesive composition described above (elongation at break, glass transition temperature of the cured product, etc.) compared to adhesive compositions obtained by other production methods.
• the adhesive composition of the present embodiment can be suitably used as an automotive adhesive used in the manufacture of automobiles, and can be more suitably used as an adhesive for motors, and can be even more suitably used as an adhesive for fixing between a magnet and a rotor (rotor) or between a magnet and a stator (fixed part) in the motor.
• the article of the present embodiment includes a cured product made of the adhesive composition of the present embodiment.
• a cured product of the adhesive composition By applying the adhesive composition of the present embodiment to an article and curing it, an article including a cured product of the adhesive composition can be obtained.
• the adhesive composition of the present embodiment can be cured (at room temperature) without heating and can bond articles (particularly when it contains a polymerization initiator and a reducing agent). Of course, the use of heat for bonding articles is not excluded.
• the motor of the present embodiment includes a cured product made of the adhesive composition of the present embodiment.
• the motor of the present embodiment includes, for example, a magnet, a rotor, and a stator, and contains a cured product of the adhesive composition of the present embodiment between at least one of the magnet and the rotor and the magnet and the stator.
• it is preferable that at least one of the magnet and the rotor and the magnet and the stator in the motor is fixed by the cured product of the adhesive composition of the present embodiment.
• a method of fixing the magnet and the rotor is to fix the magnet in a slot of the rotor.
• a method of fixing the magnet and the stator is to fix the magnet and the yoke.
• the magnet may be a ferrite magnet or a permanent magnet.
• the permanent magnet may be a neodymium magnet.
• the adhesive composition described in this specification can also be used in fields other than adhesion, for example, as a coating material or injection agent.
• the adhesive composition described in this specification can also be used as a composition with no limited use, a curable composition, or a resin composition.
• the composition of this embodiment can also be used, for example, as a so-called adhesive, sealant, photosensitive resin layer, insulating resin layer, thermally conductive resin layer, coating material, etc.
• the first and second agents were prepared by thoroughly mixing the components in the ratios (unit: parts by mass) shown in Table 1 using a stirring device equipped with a stirring blade. Equal amounts of the first and second agents were then mixed to prepare adhesive compositions. The adhesive compositions obtained were used to carry out the following evaluations. The results are shown in Table 1. Note that the units of the ratios of the components in Table 1 are all parts by mass.
• the polymerizable monomer (A) and the elastomer (B) were mixed sufficiently uniformly at 50 to 80° C. to prepare a mixture, and then other components were added to the mixture and stirred, followed by degassing treatment to prepare the first and second agents, respectively.
• BL-20 methyl methacrylate, butadiene, acrylonitrile, styrene rubber (methyl methacrylate content 15% by mass, butadiene content 46% by mass, acrylonitrile content 3% by mass, styrene content 36% by mass, soft segment unit content 46% by mass)
• 1300X33VTBNX LC acrylonitrile butadiene rubber having methacryloyl groups at both ends (acrylonitrile content 18% by mass, soft segment unit content 82% by mass)
• N250SL acrylonitrile-butadiene rubber (acrylonitrile content 19.5% by mass, soft segment unit content 81% by mass)
• DCPD type methacrylate dicyclopentanyl methacrylate
• SIPOMER PAM 4000 phosphoric acid ester of 2-hydroxyethyl methacrylate
• BPA diglycidyl ether acrylic acid adduct bisphenol A diglycidyl ether acrylic acid
• a cured product (test piece) of the adhesive composition was prepared for measuring dynamic viscoelasticity.
• the test piece was prepared as follows (1) to (3).
• the film thickness was adjusted to about 500 ⁇ m depending on the thickness of the silicone sheet.
• (3) The above sheet-like cured product was cut into rectangular test pieces measuring 0.5 ⁇ 5 ⁇ 40 mm.
• the dynamic viscoelastic properties of the obtained test specimens were measured using a dynamic viscoelasticity measuring device (DMS7100, manufactured by SII) under the following conditions: frequency: 1.0 Hz, mode: tensile mode, measurement temperature range: 0°C to 250°C, heating rate: 5°C/min, and data was obtained. Based on the obtained data, the peak top temperature of the loss tangent (tan ⁇ ) (tan ⁇ peak value, i.e., glass transition temperature) was obtained from the temperature-loss tangent (tan ⁇ ) curve.
• DMS7100 dynamic viscoelasticity measuring device
• a film was formed by applying an adhesive composition (after mixing the two-component type) to one side of one test piece (25 mm x 100 mm x 1.6 mmt cold-rolled steel plate (JIS G 3141 SPCC-SD, manufactured by Engineering Test Services Co., Ltd.), degreased with acetone), and the other test piece (25 mm x 100 mm x 1.6 mmt cold-rolled steel plate (JIS G 3141 SPCC-SD, manufactured by Engineering Test Services Co., Ltd.), degreased with acetone) was immediately superimposed on the surface of the film and bonded. Then, the test piece was aged for 24 hours at room temperature (23 ° C.). In this way, a test piece was obtained.
• a polyethylene filler manufactured by Prime Polymer Co., Ltd., product name: Hi-Zex 2100JPD
• the amount of the polyethylene filler used is 0.5 parts by mass based on 100 parts by mass of the polymerizable monomer (A).
• a tensile shear adhesion test was performed using the obtained test piece at a tensile speed of 10 mm/min in an environment of 155° C.
• a test piece with a 100 ⁇ F EOL(155) /F Ref(155) of 10% or more was evaluated as A (excellent)
• a test piece with a 100 ⁇ F EOL(155) /F Ref(155) of 5% or more but less than 10% was evaluated as B (pass)
• a test piece with a 100 ⁇ F EOL(155) /F Ref(155) of less than 5% was evaluated as C (fail).
• the tensile shear adhesive strength was measured in accordance with JIS K 6850:1999, a test method for tensile shear adhesive strength between adhesive and rigid adherend.
• test pieces prepared in the above [Thermal fatigue resistance properties] were subjected to a heat cycle test of 300 cycles, with one cycle being "treatment in an atmosphere of -10°C for 30 minutes, then treatment at room temperature for 5 minutes, then treatment at 150°C for 30 minutes, and then treatment at room temperature for another 5 minutes.”
• a tensile shear adhesion test was performed using an Instron universal testing machine Model 5967 under conditions of a temperature of 23°C, a relative humidity of 50%, and a tensile speed of 10 mm/min, and the tensile shear adhesion strength F after was measured.
• the heat cycle resistance property was evaluated by 100 x F after / F Ref (23) .
• 100 x F after / F Ref (23) of 40% or more was rated A (excellent), 20% or more but less than 40% was rated B (pass), and less than 20% was rated C (fail).
• the composition of the adhesive composition and the measurement and evaluation results are shown in Table 1.
• Table 1 the amount of each component of the adhesive composition is expressed in parts by mass.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Macromonomer-Based Addition Polymer (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=91955904

Family Applications (1)

Country Status (5)

Citations (7)

Family Cites Families (3)

• 2024
  • 2024-01-11 CN CN202480008196.0A patent/CN120548331A/zh active Pending
  • 2024-01-11 EP EP24744557.0A patent/EP4644430A4/en active Pending
  • 2024-01-11 JP JP2024571719A patent/JPWO2024154634A1/ja active Pending
  • 2024-01-11 WO PCT/JP2024/000394 patent/WO2024154634A1/ja not_active Ceased
  • 2024-01-19 TW TW113102161A patent/TW202436542A/zh unknown

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events