WO2021059972A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

Info

Publication number
WO2021059972A1
WO2021059972A1 PCT/JP2020/034007 JP2020034007W WO2021059972A1 WO 2021059972 A1 WO2021059972 A1 WO 2021059972A1 JP 2020034007 W JP2020034007 W JP 2020034007W WO 2021059972 A1 WO2021059972 A1 WO 2021059972A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
meth
polymer
weight
curable composition
Prior art date
Application number
PCT/JP2020/034007
Other languages
English (en)
Japanese (ja)
Inventor
聖 宮藤
Original Assignee
株式会社カネカ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社カネカ filed Critical 株式会社カネカ
Priority to JP2021548771A priority Critical patent/JPWO2021059972A1/ja
Publication of WO2021059972A1 publication Critical patent/WO2021059972A1/fr

Links

Classifications

    • 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
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides

Definitions

  • the present invention relates to a multi-component curable composition.
  • Vehicles, aircraft, and railroads are being replaced with lightweight materials such as aluminum, magnesium, and carbon fiber composite materials other than steel as structural members in order to reduce weight, and multi-materials that use multiple materials for one car body are becoming more common. It is increasing. Since it may be difficult to join dissimilar materials by spot welding or laser welding, adhesive joining using an adhesive is drawing attention. Since steel sheets, aluminum alloys, and fiber-reinforced composite materials have different coefficients of linear expansion, the adhesive is required to have flexibility to follow thermal strain. Therefore, an epoxy resin having high rigidity may be disadvantageous, and therefore, a material having a high elastic modulus and flexibility is required as a new structural adhesive.
  • a composition composed of a reactive silicon group-containing polyoxyalkylene polymer having high breaking strength and flexibility and an epoxy resin is known (see, for example, Patent Document 1), but is a structural member.
  • the strength may not be sufficient.
  • An adhesive composed of an organic polymer having a reactive silicon group and an epoxy resin has a low viscosity before curing, and has good workability when applied to an adherend, but has high rigidity after curing. It is required to show.
  • the present invention is a polyoxyalkylene polymer (A) having a reactive silicon group represented by the general formula (1), and a (meth) acrylic acid ester polymer having a reactive silicon group represented by the general formula (1).
  • a multi-component curable composition containing an agent A containing (B) and an epoxy resin curing agent (D) having a tertiary amine, and an agent B containing an epoxy resin (C).
  • the agent and the agent B are from sulfonic acid ester, benzoic acid ester, aliphatic carboxylic acid ether ester, dibasic acid polyester, trimellitic acid ester, epoxidized oil and fat, and C9 aromatic liquid hydrocarbon.
  • the present invention relates to a multi-component curable composition containing at least one plastic agent (E) selected from the group.
  • -SiR 5 c X 3-c (1) (Wherein, R 5 is a hydrocarbon group of a substituted or unsubstituted carbon atoms 1 ⁇ 20 .X is .c showing a hydroxyl group or a hydrolyzable group is 0 or 1.)
  • the reactive silicon group of the polyoxyalkylene polymer (A) is a trimethoxysilyl group.
  • the reactive silicon group of the (meth) acrylic acid ester polymer (B) is a trimethoxysilyl group.
  • the terminal site of the polyoxyalkylene polymer (A) is the general formula (2):
  • R 1 and R 3 are independently divalent carbon atoms 1 to 6 bonding groups, and the atoms bonded to the respective carbon atoms adjacent to R 1 and R 3 are carbon, oxygen, and nitrogen.
  • R 2 and R 4 are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
  • N is an integer of 1 to 10.
  • R 5 is a substituted or unsubstituted carbon. It is a hydrocarbon group of numbers 1 to 20.
  • X is a hydroxyl group or a hydrolyzable group. C represents 0 or 1).
  • R 1 is CH 2 OCH 2 and R 3 is CH 2 .
  • R 2 and R 4 are hydrogen atoms, respectively.
  • the (meth) acrylic acid ester-based polymer (B) has a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and a (meth) acrylic acid ester having a polymerizable unsaturated group. It is a polymer having a macromonomer (b2), which is a system polymer, as a constituent monomer.
  • the present invention is also a structural adhesive composed of the multi-component curable composition, and is also a cured product obtained by curing the multi-component curable composition.
  • a curable composition which has a low viscosity before curing but can exhibit high rigidity after curing, and a cured product obtained by curing the composition.
  • the present invention relates to a polyoxyalkylene polymer (A) having a reactive silicon group represented by the following general formula (1), and a (meth) acrylic acid ester-based polymer having a reactive silicon group represented by the following general formula (1).
  • a multi-component curable composition containing an agent A containing a coalescence (B) and an epoxy resin curing agent (D) having a tertiary amine, and an agent B containing an epoxy resin (C).
  • Agent A and Agent B are sulfonic acid esters, benzoic acid esters, aliphatic carboxylic acid ether esters, dibasic acid polyesters, trimellitic acid esters, epoxidized fats and oils, and C9-based aromatic liquid hydrocarbons.
  • the polyoxyalkylene polymer (A) having a reactive silicon group has a reactive silicon group represented by the general formula (1).
  • -SiR 5 c X 3-c (1) (Wherein, R 5 is a hydrocarbon group of a substituted or unsubstituted carbon atoms 1 ⁇ 20 .X is .c showing a hydroxyl group or a hydrolyzable group is 0 or 1.)
  • the number of carbon atoms in the hydrocarbon group for R 5 is preferably 1 to 10, more preferably 1-5, more preferably 1-3.
  • R 5 include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N, N-diethylaminomethyl group. It is preferably a methyl group, an ethyl group, a chloromethyl group or a methoxymethyl group, and more preferably a methyl group or a methoxymethyl group.
  • Examples of X include hydroxyl groups, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like.
  • an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable, because the hydrolyzability is mild and easy to handle.
  • Specific examples of the reactive silicon group contained in the polyoxyalkylene polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, and a dimethoxymethyl.
  • Cyril group diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N) , N-diethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group and the like, but are not limited thereto.
  • methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N- Diethylaminomethyl) dimethoxysilyl group is preferable because it shows high activity and a cured product having good mechanical properties can be obtained, and trimethoxysilyl group and triethoxysilyl group are more preferable because a cured product with high rigidity can be obtained.
  • a trimethoxysilyl group is more preferred.
  • the polyoxyalkylene polymer (A) may have more than one reactive silicon group on average at one terminal site. Having more than one reactive silicon group on average at one terminal site means that the polyoxyalkylene polymer (A) has 2 at one terminal site as represented by the following general formula (2). It is shown that a polyoxyalkylene having two or more reactive silicon groups is contained. That is, the polyoxyalkylene polymer (A) may contain only polyoxyalkylene having two or more reactive silicon groups at one terminal site, or two or more at one terminal site. It may contain both a polyoxyalkylene having a reactive silicon group and a polyoxyalkylene having one reactive silicon group at one terminal site.
  • the polyoxyalkylene polymer (A) as a whole is a poly having an average of more than one reactive silicon group at one terminal site, but having a terminal site having no reactive silicon group. It may contain oxyalkylene.
  • R 1 and R 3 are independently divalent carbon atoms 1 to 6 bonding groups, and the atoms bonded to the respective carbon atoms adjacent to R 1 and R 3 are carbon, oxygen, and nitrogen.
  • R 2 and R 4 are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
  • N is an integer of 1 to 10.
  • R 5 , X and c are the formulas (1). ) Is as described above.)
  • R 1 and R 3 may be divalent organic groups having 1 to 6 carbon atoms, or hydrocarbon groups that may contain oxygen atoms.
  • the hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms.
  • Specific examples of R 1 include CH 2 OCH 2 , CH 2 O, and CH 2 , but CH 2 OCH 2 is preferable.
  • Specific examples of R 3 include CH 2 and CH 2 CH 2 , but CH 2 is preferable.
  • the hydrocarbon groups of R 2 and R 4 preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms.
  • Specific examples of R 2 and R 4 include, for example, a hydrogen atom, a methyl group, and an ethyl group, but a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.
  • the terminal site represented by the general formula (2) has R 1 being CH 2 OCH 2 , R 3 being CH 2 , and R 2 and R 4 being hydrogen atoms, respectively.
  • n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • n is not limited to one value, and a plurality of values may be mixed.
  • the polyoxyalkylene polymer (A) preferably has more than 1.0 reactive silicon groups at one terminal site on average, and more preferably 1.1 or more. , 1.5 or more, more preferably 2.0 or more. Further, the number is preferably 5 or less, and more preferably 3 or less.
  • the number of terminal sites having more than one reactive silicon group contained in one molecule of the polyoxyalkylene polymer (A) is preferably 0.5 or more on average, and is 1.0.
  • the number is more preferably 1, 1.1 or more, and even more preferably 1.5 or more. Further, the number is preferably 4 or less, and more preferably 3 or less.
  • the polyoxyalkylene polymer (A) may have a reactive silicon group in addition to the terminal portion, but if it is contained only in the terminal portion, a rubber-like cured product having high elongation and low elastic modulus can be obtained. It is preferable because it is easy to get rid of.
  • the average number of reactive silicon groups contained in the polyoxyalkylene polymer (A) per molecule is preferably more than 1.0, more preferably 1.2 or more, and further 1.3 or more. Preferably, 1.5 or more are even more preferable, and 1.7 or more are particularly preferable. Further, 6.0 or less is preferable, 5.5 or less is more preferable, and 5.0 or less is most preferable. If the average number of reactive silicon groups per molecule is 1.0 or less, a high-strength cured product may not be obtained. If the average number of reactive silicon groups per molecule exceeds 6.0, a high-elongation cured product may not be obtained.
  • the main chain skeleton of the polyoxyalkylene polymer (A) is not particularly limited, and for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, etc. Examples thereof include a polyoxypropylene-polyoxybutylene copolymer. Among them, polyoxypropylene is preferable.
  • the number average molecular weight of the polyoxyalkylene polymer (A) is preferably 3,000 or more and 100,000 or less, more preferably 3,000 or more and 50,000 or less, and particularly preferably 3, in terms of polystyrene-equivalent molecular weight in GPC. It is 000 or more and 30,000 or less. If the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced increases, which may be inconvenient in terms of manufacturing cost. If it exceeds 100,000, the viscosity becomes high and workability is improved. Tends to be inconvenient.
  • the organic polymer precursor before the introduction of the reactive silicon group is prepared according to the method for measuring the hydroxyl value of JIS K 1557 and the raw material as specified in JIS K 0070. Directly measure the end group concentration by titration analysis based on the principle of the measurement method, and indicate it by the end group equivalent molecular weight obtained in consideration of the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). You can also do it.
  • the terminal group-equivalent molecular weight of the polyoxyalkylene-based polymer (A) For the terminal group-equivalent molecular weight of the polyoxyalkylene-based polymer (A), a calibration line of the number average molecular weight obtained by general GPC measurement of the organic polymer precursor and the terminal group-equivalent molecular weight is prepared, and the polyoxyalkylene-based polymer is based. It is also possible to convert the number average molecular weight of the polymer (A) obtained by GPC into the terminal group equivalent molecular weight.
  • the molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, specifically less than 2.0, more preferably 1.6 or less. 5 or less is more preferable, and 1.4 or less is particularly preferable. Further, from the viewpoint of improving various mechanical characteristics such as improving the durability and elongation of the cured product, 1.2 or less is preferable.
  • the molecular weight distribution of the polyoxyalkylene polymer (A) can be determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.
  • main chain structure of the polyoxyalkylene polymer (A) may be linear or branched.
  • the polyoxyalkylene polymer (A) having an average of more than 1.0 reactive silicon groups at one terminal site which is a preferred embodiment, is a hydroxyl group terminal polymer obtained by polymerization. It is preferable to obtain by reacting a reactive silicon group-containing compound that reacts with the carbon-carbon unsaturated bond after introducing two or more carbon-carbon unsaturated bonds into one terminal of the above.
  • the above-mentioned preferable synthesis method will be described below.
  • polymerization As the polyoxyalkylene polymer (A), a method of polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferable.
  • Examples of the initiator having a hydroxyl group include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, polyoxypropylene monoallyl ether, and polyoxypropylene monoalkyl ether. Examples thereof include those having one or more hydroxyl groups.
  • the epoxy compound examples include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Of these, propylene oxide is preferable.
  • alkali metal salt sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide and potassium ethoxide are preferable, and sodium methoxide and potassium methoxide are more preferable.
  • Sodium methoxide is particularly preferred in terms of availability.
  • the temperature at which the alkali metal salt is allowed to act is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 110 ° C. or higher and 140 ° C. or lower.
  • the time for allowing the alkali metal salt to act is preferably 10 minutes or more and 5 hours or less, and more preferably 30 minutes or more and 3 hours or less.
  • the compound represented by (R 1 and R 2 in the formula are the same as those described above) can be preferably used.
  • allyl glycidyl ether, metallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide are preferable from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferable.
  • the amount of the epoxy compound having a carbon-carbon unsaturated bond added can be any amount in consideration of the amount of the carbon-carbon unsaturated bond introduced into the polymer and the reactivity.
  • the molar ratio of the hydroxyl-terminated polymer to the hydroxyl group is preferably 0.2 or more, more preferably 0.5 or more. Further, it is preferably 5.0 or less, and more preferably 2.0 or less.
  • the reaction temperature at the time of cycloaddition reaction of an epoxy compound having a carbon-carbon unsaturated bond with a polymer containing a hydroxyl group is preferably 60 ° C. or higher and 150 ° C. or lower, preferably 110 ° C. or higher. It is more preferably 140 ° C. or lower.
  • halogenated hydrocarbon compound having a carbon-carbon unsaturated bond examples include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. It is more preferable to use allyl chloride or metallyl chloride from the viewpoint of ease of handling.
  • the amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond added is not particularly limited, but the molar ratio of the hydroxyl-terminated polymer to the hydroxyl group is preferably 0.7 or more, more preferably 1.0 or more. .. Further, 5.0 or less is preferable, and 2.0 or less is more preferable.
  • the temperature at which the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 110 ° C. or higher and 140 ° C. or lower.
  • the reaction time is preferably 10 minutes or more and 5 hours or less, and more preferably 30 minutes or more and 3 hours or less.
  • the method for introducing the reactive silicon group is not particularly limited, and a known method can be used. The introduction method is illustrated below.
  • Examples of the group capable of forming a bond by reacting with a carbon-carbon unsaturated bond include, but are not limited to, a mercapto group.
  • a method for reacting a reactive group-containing polymer with a silane coupling agent includes a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, an amino group and an epoxy group, and an amino.
  • Examples include, but are not limited to, a group and an ⁇ , ⁇ -unsaturated carbonyl group (reaction by Michael addition), a carboxy group and an epoxy group, an unsaturated bond and a mercapto group.
  • the method (i) is preferable because the reaction is simple, the amount of the reactive silicon group introduced is adjusted, and the physical properties of the obtained reactive silicon group-containing polyoxyalkylene polymer (A) are stable.
  • the methods (ii) and (iii) have many reaction options, and it is easy to increase the rate of introduction of reactive silicon groups, which is preferable.
  • the hydrosilane compound that can be used in the method (i) is not particularly limited, but for example, trimethoxysilane, triethoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, etc. Dimethoxyethylsilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) diethoxysilane, (N, N-diethylaminomethyl) dimethoxysilane, (N, N- Diethylaminomethyl) diethoxysilane and the like.
  • the amount of the hydrosilane compound used is such that the molar ratio (number of moles of hydrosilane / number of moles of carbon-carbon unsaturated bond) to carbon-carbon unsaturated bond in the polymer that is the precursor is 0.05 or more and 10 or less. It is preferable from the viewpoint of reactivity, and more preferably 0.3 or more and 2 or less from the viewpoint of economy.
  • the hydrosilylation reaction is accelerated by various catalysts.
  • known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium may be used.
  • a carrier in which platinum is supported on a carrier such as alumina, silica, or carbon black, platinum chloride acid; a platinum chloride acid complex composed of platinum chloride acid and alcohol, aldehyde, ketone, or the like; a platinum-olefin complex [for example, Pt (CH).
  • Platinum-vinylsiloxane complex [Pt ⁇ (vinyl) Me 2 SiOSiMe 2 (vinyl) ⁇ , Pt ⁇ Me (vinyl) SiO ⁇ 4 ]; Platinum-phosphine complex [Ph (PPh 3 ) 4 , Pt (PBu 3 ) 4 ]; Platinum-phosphite complex [Pt ⁇ P (OPh) 3 ⁇ 4 ] and the like can be used. From the viewpoint of reaction efficiency, it is preferable to use a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.
  • silane coupling agent examples include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and 3-mercaptopropyltri that react with unsaturated bonds.
  • Mercaptosilanes such as ethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyldimethoxymethylsilane; 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, isocyanate that react with hydroxylates.
  • Isocyanate silanes such as methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxy, which react with hydroxyl groups, amino groups or carboxy groups.
  • Epoxysilanes such as methylsilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane; react with isocyanate groups or thioisocyanate groups 3-Aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) propyltrimethoxysilane, 3- (2-aminoethyl) propyldimethoxymethyl Silane, 3- (2-aminoethyl) propyltriethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimeth
  • the main chain of the polyoxyalkylene polymer (A) may be an ester bond or a general formula (4): as long as the effects of the invention are not impaired.
  • the cured product obtained from the curable composition containing the polyoxyalkylene polymer (A) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonds and the like.
  • the polyoxyalkylene polymer (A) containing an amide segment or the like may be cleaved by heat or the like.
  • the curable composition containing the polyoxyalkylene polymer (A) containing an amide segment or the like tends to have a high viscosity.
  • the polyoxyalkylene-based polymer (A) may be a polyoxyalkylene containing an amide segment or the like, or a polyoxyalkylene containing no amide segment or the like may be used. You may.
  • Examples of the amide segment represented by the general formula (4) include a reaction between an isocyanate group and a hydroxyl group, a reaction between an amino group and a carbonate, a reaction between an isocyanate group and an amino group, and a reaction between an isocyanate group and a mercapto group. Etc. can be mentioned. Further, those formed by the reaction of the amide segment containing an active hydrogen atom with an isocyanate group are also included in the amide segment represented by the general formula (4).
  • Z is a hydroxyl group
  • a method of reacting the Z group of a silicon compound represented by a carboxy group, a mercapto group, a primary amino group or a secondary amino group) with all or a part of the isocyanate groups of the synthesized polymer can be mentioned. it can.
  • the silicon compound represented by the general formula (5) is not particularly limited, but for example, ⁇ -aminopropyldimethoxymethylsilane, ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -amino.
  • Amino group-containing silanes such as propyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyldimethoxymethylsilane, (N-phenyl) - ⁇ -aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane Classes; hydroxyl group-containing silanes such as ⁇ -hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as ⁇ -mercaptopropyltrimethoxysilane and mercaptomethyltriethoxysilane; and the like.
  • JP-A-6-21179 US Patent No.
  • the reactive silicon group-containing isocyanate compound represented by the general formula (6) is not particularly limited, and for example, ⁇ -trimethoxysilylpropyl isocyanate, ⁇ -triethoxysilylpropyl isocyanate, ⁇ -methyldimethoxysilylpropyl isocyanate, etc.
  • ⁇ -Methyldiethoxysilylpropyl isocyanate ⁇ - (methoxymethyl) dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (methoxymethyl) Examples thereof include dimethoxysilylmethyl isocyanate.
  • the number of amide segments (average value) per molecule of the polyoxyalkylene polymer (A) is preferably 1 to 10, preferably 1.5 to 5. Is more preferable, and 2 to 3 are particularly preferable. If this number is less than 1, the curability may not be sufficient, and conversely, if it is more than 10, the polyoxyalkylene polymer (A) may have a high viscosity and become difficult to handle. There is. In order to reduce the viscosity of the curable composition and improve workability, the polyoxyalkylene polymer (A) preferably does not contain an amide segment.
  • (meth) acrylic acid ester-based monomer constituting the main chain of a reactive silicon group-containing (meth) acrylic acid ester-based polymer (B) (also referred to as "(meth) acrylic acid ester-based polymer (B)") Is not particularly limited, and various types can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate.
  • Examples of the monomer unit other than the above include acrylic acids such as acrylic acid and methacrylic acid; monomers containing an amide group such as N-methylolacrylamide and N-methylolmethacrylate, glycidyl acrylate and glycidyl methacrylate. , Epoxy group-containing monomer, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and the like, nitrogen-containing group-containing monomer and the like.
  • the (meth) acrylic acid ester-based polymer (B) a polymer obtained by copolymerizing a (meth) acrylic acid ester-based monomer and a vinyl-based monomer copolymerizable therewith can also be used.
  • the vinyl-based monomer is not particularly limited, and is, for example, a styrene-based monomer such as styrene, vinyl toluene, ⁇ -methylstyrene, chlorostyrene, styrenesulfonic acid and a salt thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride and the like.
  • Fluorine-containing vinyl-based monomers Silicon-containing vinyl-based monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; monoalkyl esters of fumaric acid and fumaric acid And dialkyl esters; maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile.
  • Vinyl-containing monomer amide group-containing vinyl-based monomer such as acrylamide and methacrylicamide; Vinyl ester-based monomer such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl laurate; alkenyl-based monomer such as ethylene and propylene Monomers; conjugated diene-based monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like, and a plurality of these can be used as copolymerization components.
  • amide group-containing vinyl-based monomer such as acrylamide and methacrylicamide
  • Vinyl ester-based monomer such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl laurate
  • alkenyl-based monomer such as ethylene and propylene Monomers
  • conjugated diene-based monomers such as butadiene and isoprene
  • (meth) acrylic acid ester-based polymers obtained from the monomers a copolymer composed of a (meth) acrylic acid ester-based monomer and, in some cases, a styrene-based monomer is preferable because of its excellent physical properties.
  • a (meth) acrylic acid ester-based polymer composed of an acid ester monomer and a methacrylic acid ester monomer is more preferable, and an acrylic acid ester-based polymer composed of an acrylic acid ester monomer is particularly preferable.
  • the (meth) acrylic acid ester-based polymer (B) has a reactive silicon group represented by the general formula (1) shown above.
  • the reactive silicon group of the (meth) acrylic acid ester-based polymer (B) may be the same as or different from the reactive silicon group of the polyoxyalkylene-based polymer (A).
  • Specific examples of R 5 include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N, N-diethylaminomethyl group, but a methyl group and an ethyl group are preferable.
  • Examples of X include hydroxyl groups, hydrogens, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like.
  • an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable because the hydrolysis property is mild and easy to handle.
  • reactive silicon group contained in the (meth) acrylic acid ester-based polymer (B) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, and a triacetoxysilyl group.
  • methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N- Diethylaminomethyl) dimethoxysilyl group is preferable because it shows high activity and a cured product having good mechanical properties can be obtained, and trimethoxysilyl group and triethoxysilyl group are more preferable because a cured product having a high young rate can be obtained. , Trimethoxysilyl group is more preferable.
  • the reactive silicon group equivalent of the (meth) acrylic acid ester polymer (B) is not particularly limited, but is preferably 0.1 mmol / g or more, more preferably 0.5 mmol / g or more, and 0.6 mmol / g or more. Is even more preferable.
  • the reactive silicon group equivalent is preferably 2.0 mmol / g or less, and more preferably 1.0 mmol / g or less from the viewpoint of suppressing a decrease in elongation of the cured product. Further, in order to obtain a highly rigid cured product having a high Young's modulus, the reactive silicon group equivalent is particularly preferably 0.6 mmol / g or more and 1.0 mmol / g or less.
  • the method for introducing a reactive silicon group into the (meth) acrylic acid ester-based polymer is not particularly limited, and for example, the following method can be used.
  • (Iv) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive silicon-containing group together with the above-mentioned monomer. Using this method, reactive silicon groups tend to be randomly introduced into the main chain of the polymer.
  • (V) A method for polymerizing a (meth) acrylic acid ester-based polymer using a mercaptosilane compound having a reactive silicon-containing group as a chain transfer agent. By using this method, a reactive silicon group can be introduced into the polymer terminal.
  • Vi A method in which a compound having a polymerizable unsaturated group and a reactive functional group (V group) is copolymerized, and then the compound having a reactive silicon group and a functional group that reacts with the V group is reacted.
  • a method of copolymerizing 2-hydroxyethyl acrylate and then reacting with an isocyanate silane having a reactive silicon-containing group, or an aminosilane compound having a reactive silicon-containing group after copolymerizing glycidyl acrylate. Can be exemplified as a method of reacting.
  • (Vii) A method for introducing a reactive silicon group by modifying the terminal functional group of the (meth) acrylic acid ester-based polymer synthesized by the living radical polymerization method.
  • the (meth) acrylic acid ester-based polymer obtained by the living radical polymerization method can easily introduce a functional group at the polymer terminal, and by modifying this, a reactive silicon group can be introduced at the polymer terminal.
  • Examples of the silicon compound that can be used to introduce the reactive silicon group of the (meth) acrylic acid ester-based polymer (B) by using the above method include the following compounds.
  • Examples of the compound having a polymerizable unsaturated group and a reactive silicon-containing group used in the method (iv) include 3- (dimethoxymethylsilyl) propyl (meth) acrylate and 3- (trimethoxysilyl) (meth) acrylate.
  • Examples of the mercaptosilane compound having a reactive silicon-containing group used in the method (v) include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl) dimethoxymethylsilane, and (mercaptomethyl) trimethoxy.
  • Examples include silane.
  • Examples of the compound having a reactive silicon group and a functional group that reacts with the V group used in the method (vi) include 3-isocyanapropyldimethoxymethylsilane, 3-isocyanuppropyltrimethoxysilane, and 3-isocyanuppropyltriethoxysilane.
  • Isoisocyanate compounds such as isocyanate methyldimethoxymethylsilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane; 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri Epoxysilane compounds such as ethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyldimethoxymethylsilane, glycidoxymethyltriethoxysilane; 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, aminomethyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, N-cyclohexylaminomethyldimethoxymethylsilane, N-cyclohe
  • any modification reaction can be used.
  • a method using a compound having a functional group capable of reacting with the terminal reactive group obtained by polymerization and a reactive silicon group a method using a terminal reactive group, and the like.
  • a method can be used in which a double bond is introduced at the terminal of the polymer using a compound having a reactive functional group and a double bond, and a reactive silicon group is introduced into the double bond by hydrosilylation or the like.
  • the (meth) acrylic acid ester-based polymer (B) often contains a polymer containing 40% by weight or more of the alkyl (meth) acrylic acid having 1 to 3 carbon atoms in all the monomers. It is preferable because it becomes rigid.
  • the (meth) acrylic acid ester-based polymer (B) is composed of only a polymer containing 40% by weight or more of the (meth) acrylic acid alkyl having 1 to 3 carbon atoms in the alkyl. Although it may be present, a polymer containing 40% by weight or more of alkyl (meth) acrylate having 4 to 30 carbon atoms of alkyl in the total monomer is also contained together with the polymer, and both are blended. This is preferable because it improves rigidity, elongation, and strength.
  • the (meth) acrylic acid ester-based polymer (B) contains 40% by weight or more of the alkyl (meth) acrylic acid having 1 to 3 carbon atoms and 4 to 4 to 3 alkyl carbon atoms in the total monomer. It is also preferable to contain a polymer obtained by copolymerizing a monomer mixture containing 40% by weight or more of alkyl (meth) acrylate in all the monomers because the rigidity, elongation and strength are improved.
  • the (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer is a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group represented by the above-mentioned general formula (1).
  • a polymer having a macromonomer (b2) which is a (meth) acrylic acid ester-based polymer having a polymerizable unsaturated group, as a constituent monomer.
  • the polymer may further contain (meth) acrylic acid alkyl ester (b3) having 1 to 3 carbon atoms as a constituent monomer.
  • "(meth) acrylic” means "acrylic and / or methacrylic".
  • Polymer having a reactive silicon group and a polymerizable unsaturated group (b1) examples include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, and 3-(.
  • Compounds having a (meth) acryloxy group and a reactive silicon group such as (meth) acryloxypropyldimethoxymethylsilane, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyldimethoxymethylsilane; vinyltrimethoxysilane, vinyl Examples thereof include compounds having a vinyl group such as triethoxysilane and a reactive silicon group. Only one of these compounds may be used, or two or more of these compounds may be used in combination.
  • the total content of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group is the total content of the (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer (b2). It is preferably 0.1% by weight or more and 50% by weight or less, more preferably 0.5% by weight or more and 30% by weight or less, and even more preferably 1% by weight or more and 20% by weight or less with respect to the monomer.
  • the macromonomer (b2) is a (meth) acrylic acid ester-based polymer having a polymerizable unsaturated group.
  • the macromonomer (b2) itself is a polymer, it can be copolymerized with a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group by the polymerizable unsaturated group. It is a monomer constituting the (meth) acrylic acid ester-based polymer (B).
  • the main chain skeleton of the macromonomer (b2) is a (meth) acrylic acid ester-based polymer.
  • the monomer constituting the main chain skeleton of the macromonomer (b2) is not particularly limited, and various types can be used.
  • Examples of the (meth) acrylic monomer include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and isopropyl (meth) acrylic acid.
  • N-Butyl (meth) acrylate Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, Cyclohexyl (meth) acrylate, (meth) N-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) Stearyl acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, (meth) acrylate 2-Hyd
  • styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, and styrenesulfonic acid
  • fluorine-containing vinyls such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
  • Styrene Styrene; maleic acid such as maleic acid, maleic anhydride, maleic acid monoalkyl ester, maleic acid dialkyl ester and its derivatives; fumaric acid such as fumaric acid, fumaric acid monoalkyl ester and fumaric acid dialkyl ester and derivatives thereof; Maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; vinyl acetate, vinyl propionate, vinyl pivalate, etc.
  • maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, oct
  • Vinyl ester-based monomers such as vinyl benzoate and vinyl cinnate; olefin-based monomers such as ethylene and propylene; conjugated diene-based monomers such as butadiene and isoprene; (meth) acrylamide; (meth) acrylonitrile; chloride
  • vinyl-based monomers such as vinyl, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether, and butyl vinyl ether. Only one type of other monomer may be used, or two or more types may be used in combination.
  • the macromonomer (b2) has a polymerizable unsaturated group, which exhibits polymerizable properties.
  • the polymerizable unsaturated group may be introduced into either the molecular chain end or the side chain of the (meth) acrylic acid ester-based polymer, but from the viewpoint of adhesiveness, the molecular chain end. It is preferable that it is introduced in.
  • the polymerizable unsaturated group of the macromonomer (b2) is not particularly limited as long as it is an unsaturated group exhibiting polymerizable properties in a general radical polymerization method.
  • Acryloyl group and methacryloyl group are preferable because they show good polymerizable property.
  • the method for introducing a polymerizable unsaturated group into the macromonomer (b2) is not particularly limited, and for example, the methods shown in (viii) to (x) below can be used.
  • (Viii) A method of copolymerizing a monomer having two kinds of polymerizable unsaturated groups having different reactivity (for example, allyl acrylate) together with a monomer having a (meth) acrylic structure.
  • Z group for example, acrylic acid, 2-hydroxyethyl acrylate
  • a method of reacting a compound having a sex unsaturated group and a functional group that reacts with a Z group for example, diethyl isocyanate (meth) acrylate.
  • a Z group for example, diethyl isocyanate (meth) acrylate.
  • the method (x) is preferably used because a polymerizable unsaturated group can be introduced at the end of the molecular chain.
  • the "living radical polymerization method” uses, for example, a cobalt porphyrin complex as shown in the Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, Vol. 116, p. 7943. Those using nitrooxide radicals as shown in Japanese Patent Application Laid-Open No. 2003-570378, organic halides and halogenated sulfonyl compounds as shown in JP-A-11-130931 are used as initiators. , Atom transfer radical polymerization (ATRP method) using a transition metal complex as a catalyst, and the like. The atom transfer radical polymerization method is most preferable because it is easy to introduce a polymerizable unsaturated group at the terminal.
  • the polymerizable unsaturated group of the macromonomer (b2) preferably has a structure represented by the following general formula (7).
  • CH 2 C (R 8 ) -COO-Z (7)
  • R 8 represents a hydrogen or methyl group.
  • Z represents the main clavicle of the macromonomer (b2).
  • the number average molecular weight of the macromonomer (b2) is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and preferably 50,000 or less, more preferably 30,000. It is as follows. When the number average molecular weight of the macromonomer (b2) is small, the viscosity of the (meth) acrylic acid ester-based polymer (B) is low, but good adhesiveness tends not to be obtained. On the other hand, if the number average molecular weight of the macromonomer (b2) is too large, the viscosity tends to be too high and handling tends to be difficult.
  • the molecular weight distribution of the macromonomer (b2) is not particularly limited, but is preferably narrow, more preferably less than 2.0, still more preferably 1.6 or less. 1.5 or less is particularly preferable, 1.4 or less is more particularly preferable, 1.3 or less is even more preferable, and 1.2 or less is most preferable.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) of the macromonomer (b2) are values measured by GPC (polystyrene conversion), and detailed measurement methods thereof will be described in Examples.
  • the (meth) acrylic acid ester-based polymer (B) is composed of a macromonomer (b2) and other monomers, and the main chain of the (meth) acrylic acid ester-based polymer (B) is a trunk chain.
  • a polymer chain derived from the macromonomer (b2) and branched from the trunk chain is called a branched chain.
  • the monomer constituting the trunk chain and the branch chain is composed of the above-mentioned monomers and is not particularly limited. It is preferable that the Tg of the branch chain is lower than the Tg of the trunk chain because good adhesiveness can be obtained.
  • the Tg of the trunk chain is preferably ⁇ 60 ° C. to 150 ° C., more preferably 0 ° C. to 130 ° C., and even more preferably 30 ° C. to 100 ° C.
  • the Tg of the branch chain is preferably ⁇ 100 ° C. to 150 ° C., more preferably ⁇ 90 ° C. to 100 ° C., and even more preferably ⁇ 80 ° C. to 50 ° C.
  • Tg is obtained from the following Fox formula.
  • Fox formula: 1 / (Tg (K)) ⁇ (Mi / Tgi) (In the formula, Mi represents the weight fraction of the monomer i component constituting the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of the monomer i.)
  • Tg glass transition temperature
  • the total content of the macromonomer (b2) is preferably 1% by weight or more and 50% by weight or less, and 5% by weight or more and 40% by weight, based on all the monomers constituting the (meth) acrylic acid ester-based polymer (B).
  • the following is more preferable, and 10% by weight or more and 30% by weight or less is even more preferable.
  • the macromonomer (b2) may be introduced into either the molecular chain end or the side chain of the (meth) acrylic acid ester polymer (B), but it must be introduced into the side chain from the viewpoint of adhesiveness. Is preferable.
  • the number of macromonomers contained in one molecule of the (meth) acrylic acid ester-based polymer (B) is, on average, preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more. Further, it is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.3 or less.
  • the alkyl group constituting the (meth) acrylic acid alkyl ester (b3) has 1 to 3 carbon atoms.
  • Specific examples of the (b3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Only one type of these may be used, or two or more types may be used in combination.
  • the total content of the (meth) acrylic acid alkyl ester (b3) is the (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer (b2) from the viewpoint of achieving both flexibility and high rigidity. It is preferably 40% by weight or more, more preferably 45% by weight or more, further preferably 50% by weight or more, still more preferably 55% by weight or more, based on all the constituent monomers. , 60% by weight or more is more preferable. Further, from the viewpoint of durable adhesiveness, it is preferably 50% by weight or more, more preferably 55% by weight or more, based on all the monomers constituting the (meth) acrylic acid ester-based polymer (B). , 60% by weight or more is more preferable. In order to ensure compatibility with the polyoxyalkylene polymer (A), it is preferably 70% by weight or less, and more preferably 65% by weight or less.
  • the (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer (b2) is at least a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and a macromonomer (b2).
  • a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group and a macromonomer (b2).
  • ) Is a constituent monomer, but contains (meth) acrylic acid alkyl ester (b3) having 1 to 3 carbon atoms of alkyl and a monomer other than these as a constituent monomer. You may. Specific examples of such monomers include (meth) acrylic monomers that do not fall under (b1) to (b3) and monomers other than (meth) acrylic monomers. It is possible to use various monomers exemplified for the macromonomer (b2).
  • the (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer (b2) uses a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group with another monomer. It is synthesized by copolymerization. As a result, reactive silicon groups can be randomly introduced into the main chain of the polymer. However, in order to further introduce a reactive silicon group into the (meth) acrylic acid ester-based polymer (B), the above-mentioned method can also be used in combination.
  • the monomer composition of the (meth) acrylic acid ester-based polymer (B) can be selected depending on the application and purpose, and in applications requiring strength, those having a relatively high glass transition temperature (Tg) are preferable. , 0 ° C. or higher and 200 ° C. or lower is preferable, and those having Tg of 20 ° C. or higher and 100 ° C. or lower are more preferable. Tg can be obtained from the Fox formula described above.
  • the number average molecular weight of the (meth) acrylic acid ester-based polymer (B) is not particularly limited, but the polystyrene-equivalent molecular weight measured by GPC is preferably 500 or more and 50,000 or less, more preferably 500 or more and 30,000 or less. It is particularly preferable that it is 000 or more and 10,000 or less. Among them, the number average molecular weight of the (meth) acrylic acid ester-based polymer (B) is preferably 3000 or less because it exhibits good adhesiveness even after the moist heat resistance test.
  • the method for blending the (meth) acrylic acid ester-based polymer (B) and the polyoxyalkylene-based polymer (A) is described in JP-A-59-122541, JP-A-63-112642, and JP-A-6-. It is proposed in Japanese Patent Application Laid-Open No. 172631 and Japanese Patent Application Laid-Open No. 11-116763.
  • a method of polymerizing a (meth) acrylic acid ester-based monomer in the presence of a polyoxypropylene-based polymer having a reactive silicon group can be used.
  • the weight ratio (A): (B) of the polyoxyalkylene polymer (A) to the (meth) acrylic acid ester polymer (B) is 95: 5 to 50:50, that is, (A) and ( The ratio of (A) to the total of B) is preferably 50% by weight or more and 95% by weight or less. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained. Further, in terms of achieving both high rigidity and flexibility, (A): (B) is preferably 80:20 to 50:50, and more preferably 70:30 to 50:50.
  • Epoxy resin (C) examples include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant epoxy resin such as tetrabromobisphenol A glycidyl ether, novolac type epoxy resin, and hydrogenated bisphenol A type epoxy resin.
  • Examples thereof include epoxiates of unsaturated polymers such as, but the present invention is not limited to these, and commonly used epoxy resins can be used.
  • An epoxy resin having at least two epoxy groups in one molecule is preferable because it has high reactivity during curing and the cured product easily forms a three-dimensional network. More preferable ones include bisphenol A type epoxy resins and novolak type epoxy resins.
  • the amount of the epoxy resin (C) used is the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B) and the weight ratio of the epoxy resin (C) [(A) + ( B)]: (C) is 90:10 to 50:50, that is, the ratio of [(A) + (B)] to the total of (A) to (C) is 50% by weight or more and 90 weight. It is preferable to use it so as to be% or less.
  • the ratio of [(A) + (B)] is larger than 90% by weight, the strength is lowered, and when it is smaller than 50% by weight, the flexibility is lowered and the hardness becomes too hard. Further, 80:20 to 60:40 is more preferable in terms of the balance between flexibility and strength.
  • Young's modulus is an index indicating rigidity
  • Young's modulus indicated by a cured product obtained by curing the curable composition according to the present embodiment is the polyoxyalkylene polymer (A) and (meth) acrylic specified in the present application. It can be arbitrarily adjusted by the weight ratio of the acid ester polymer (B) and the epoxy resin (C).
  • (A): (B) is set to 95: 5 to 60:40
  • (A): (B) is set to 80:20 to 50:50, and [(A) + (B)] :( C. ) Is preferably 70:30 to 50:50.
  • Epoxy resin curing agent (D) having a tertiary amine As the epoxy resin curing agent (D) for curing the epoxy resin (C), it is preferable to use an epoxy resin curing agent having a tertiary amine. By using the epoxy resin curing agent (D) having a tertiary amine, a cured product having high rigidity, high strength and high elongation can be obtained.
  • any compound having a tertiary amine can be used. Specifically, for example, N, N, N', N'-tetramethyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,6-diaminohexane, N, N.
  • -Dimethylbenzylamine N-methyl-N- (dimethylaminopropyl) aminoethanol, (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tripropylamine, DBU, DBN and these Salts of tertiary amines can be exemplified, but are not limited thereto. Further, two or more kinds may be used in combination, or a known epoxy resin curing agent other than the component (D) may be further added.
  • the epoxy resin curing agent (D) having a tertiary amine is preferably an aromatic amine, and more preferably has three or more amino groups. Specifically, 2,4,6-tris (dimethylaminomethyl) phenol can be exemplified.
  • the amount of the epoxy resin curing agent (D) used is preferably 0.1 parts by weight or more and 50 parts by weight or less, and 0.1 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the epoxy resin (C). It is more preferable that the amount is 0.5 parts by weight or more and 30 parts by weight or less.
  • Plasticizer (E) has an action of lowering the viscosity of the agent by being blended with either or both of the agent A and the agent B.
  • plasticizer (E) by using a specific plasticizer as the plasticizer (E), it is possible to reduce the viscosity before curing and to realize high rigidity after curing.
  • the plasticizer (E) is selected from the group consisting of sulfonic acid ester, benzoic acid ester, aliphatic carboxylic acid ether ester, dibasic acid polyester, trimellitic acid ester, epoxidized oil and fat, and C9-based aromatic liquid hydrocarbon. Use at least one of the following. Of these, benzoic acid ester, aliphatic carboxylic acid ether ester, trimellitic acid ester, and epoxidized fat and oil are preferable because high rigidity can be realized after curing. Benzoic acid ester, trimellitic acid ester, and epoxidized fats and oils are preferable because high rigidity can be obtained even at 50 ° C. or higher.
  • sulfonic acid ester examples include an alkyl sulfonic acid ester, a phenyl sulfonic acid ester, and an alkyl sulfonic acid phenyl ester.
  • benzoic acid ester examples include benzoic acid alkyl ester, benzoic acid ether ester, benzoic acid glycol ester and the like, and benzoic acid ether ester and benzoic acid glycol ester are preferable.
  • Benzoic acid ether ester is a condensate of benzoic acid and an alcohol having an ether structure.
  • the alcohol having an ether structure examples include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2- (2-butoxyethoxy) ethanol, polyethylene glycol, polypropylene glycol and the like.
  • Benzoic acid glycol ester is a polycondensate of benzoic acid and aliphatic glycol.
  • Examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol.
  • Examples thereof include neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, etc., and one or more of these may be mixed. May be used.
  • the aliphatic carboxylic acid ether ester is a condensate of an aliphatic monobasic acid or an aliphatic dibasic acid and an alcohol having an ether structure.
  • the aliphatic monobasic acid include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid and the like.
  • Examples of the aliphatic dibasic acid include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like.
  • Examples of the alcohol having an ether structure include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2- (2-butoxyethoxy) ethanol, polyethylene glycol, polypropylene glycol and the like.
  • Examples of the aliphatic monobasic acid ether ester include polyethylene glycol dioctate (product name; monosizer W-262 manufactured by DIC Corporation).
  • Examples of the aliphatic dibasic acid ether ester include bis adipate (2-butoxyethyl) (product name: D931 manufactured by J-Plus Co., Ltd.) and bis adipate [2- (2-butoxyethoxy) ethyl]. (Product name: BXA-N manufactured by Daihachi Chemical Industry Co., Ltd.), dibutyldiglycol adipate (product name; monosizer W-260 manufactured by DIC Co., Ltd.) and the like can be mentioned.
  • the dibasic acid polyester is a polycondensate of dibasic acid and an aliphatic glycol.
  • the dibasic acid include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.
  • the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol.
  • Examples thereof include neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, etc., and one or more of these may be mixed. May be used.
  • trimellitic acid ester examples include tristrimellitic acid (2-ethylhexyl) (product name: ADEKA Sizer C-8, manufactured by ADEKA Corporation) and trisoctyl trimellitic acid (product name: monosizer W-755 DIC). (Manufactured by Co., Ltd.) and the like.
  • the epoxidized fat and oil is an epoxidized natural fat and oil or fatty acid ester.
  • natural fats and oils various natural fats and oils can be used, and examples thereof include soybean oil, flax oil, safflower oil, sunflower oil, corn oil, and rapeseed oil. Of these, soybean oil, flax oil, and rapeseed oil are preferable.
  • Specific examples of the epoxidized fats and oils of natural fats and oils include epoxidized Amani oil (product name; ADEKA Sizer O-180A manufactured by ADEKA Corporation) and epoxidized rapeseed fatty acid isobutyl (product name: ADEKA Sizer D-55). ADEKA Corporation) and the like.
  • Specific examples of the epoxidized fat and oil of the fatty acid ester include an epoxidized fatty acid ester (product name; Eposizer W-121 manufactured by DIC Co., Ltd.) and the like.
  • the C9-based aromatic liquid hydrocarbon is a hydrocarbon resin mainly composed of ⁇ -methylstyrene, which is a resin obtained by copolymerizing ⁇ -methylstyrene with an aromatic compound such as styrene or phenol.
  • NOVALES L100, NOVALES LA-300, NOVALES HA-1100 all manufactured by RUTGERS
  • those having a low hydroxyl group content are preferable, those having a hydroxyl group content of 5% or less are preferable, those having a hydroxyl group content of 3% or less are more preferable, and those having a hydroxyl group content of 1% or less are further preferable.
  • NOVALES L100 is preferable.
  • the amount of the plasticizer (E) used is 100% by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). It is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, and further preferably 7 parts by weight or more. Further, it is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and further preferably 30 parts by weight or less.
  • the amount of the plasticizer (E) used is preferably 2 parts by weight or more, preferably 3 parts by weight or more, based on 100 parts by weight of the epoxy resin (C). More preferably, it is more preferably 5 parts by weight or more. Further, it is preferably 80 parts by weight or less, preferably 60 parts by weight or less, and further preferably 45 parts by weight or less.
  • silanol condensation catalyst for the purpose of accelerating the reaction of condensing the reactive silicon groups of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B) and extending or cross-linking the polymer. It is preferable to use F).
  • silanol condensation catalyst (F) examples include organotin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.
  • organic tin compound examples include dibutyl tin dilaurate, dibutyl tin dioctanoate, dibutyl tin bis (butyl maleate), dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), and dioctyl tin bis (acetylacetate).
  • dioctyl tin dilaurate dioctyl tin distearate, dioctyl tin diacetate, dioctyl tin oxide, reaction product of dibutyl tin oxide and silicate compound, reaction product of dioctyl tin oxide and silicate compound, dibutyl tin oxide and phthalate ester Examples include the reactants of.
  • metal carboxylate salt examples include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate and the like.
  • carboxylic acid metal salt the following carboxylic acids and various metals can be combined.
  • amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; pyridine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,5. -Nitrogen-containing heterocyclic compounds such as diazabicyclo [4,3,0] nonen-5 (DBN); guanidines such as guanidine, phenylguanidine, diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide and 1-phenylbiguanide. Biguanides such as; amino group-containing silane coupling agent; ketimine compound and the like.
  • carboxylic acid examples include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
  • alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxytitanium bis (ethylacetatete), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetate.
  • titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxytitanium bis (ethylacetatete), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetate.
  • aluminum compounds such as, and zirconium compounds such as zirconium tetrakis (acetylacetonate).
  • the amount used is 0. 0 parts by weight based on a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). It is preferably 001 parts by weight or more and 20 parts by weight or less, more preferably 0.01 parts by weight or more and 15 parts by weight or less, and further preferably 0.01 parts by weight or more and 10 parts by weight or less.
  • Water (G) may be added to the agent B of the curable composition. By adding water, the curing of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B) is promoted when the agent A and the agent B are mixed.
  • the amount of water (G) added is 0.1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). Is more preferable, 0.1 parts by weight or more and 5 parts by weight or less is more preferable, and 0.1 parts by weight or more and 2 parts by weight or less is further preferable.
  • the curable composition may contain an agent C containing water (G) in addition to the agent A and the agent B. In this case, the curable composition is a three-component type.
  • the curable composition includes a polyoxyalkylene polymer (A), a (meth) acrylic acid ester polymer (B), an epoxy resin (C), an epoxy resin curing agent (D), a plasticizer (E), and the like.
  • A polyoxyalkylene polymer
  • B acrylic acid ester polymer
  • C epoxy resin
  • D epoxy resin curing agent
  • E plasticizer
  • F silanol condensation catalyst
  • G water
  • additives fillers, adhesiveness-imparting agents, sagging inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, tackifier resins, and other resins May be added.
  • various additives may be added to the curable composition, if necessary, for the purpose of adjusting various physical properties of the curable composition or the cured product.
  • additives examples include solvents, diluents, photocurable substances, oxygen curable substances, surface improvers, silicates, curable modifiers, radical inhibitors, metal deactivators, ozone.
  • solvents examples include solvents, diluents, photocurable substances, oxygen curable substances, surface improvers, silicates, curable modifiers, radical inhibitors, metal deactivators, ozone.
  • deterioration inhibitors include deterioration inhibitors, phosphorus-based peroxide decomposing agents, lubricants, pigments, mold inhibitors, flame retardants, and foaming agents.
  • Fillers include heavy calcium carbonate, collagen carbonate, magnesium carbonate, silicic acid, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, molten silica, silicic acid anhydride, and hydrous silicic acid.
  • Examples thereof include alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament. It is more preferable to use fumed silica because thixotropic property can be efficiently imparted. Since the Young's modulus can be increased, it is preferable to use glued calcium carbonate and molten silica.
  • the amount of the filler used is preferably 1 to 300 parts by weight, preferably 10 to 250 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). The portion is more preferable.
  • Organic balloons and inorganic balloons may be added for the purpose of reducing the weight (lower specific gravity) of the composition.
  • An adhesiveness-imparting agent can be added to the curable composition.
  • a silane coupling agent and a reaction product of the silane coupling agent can be added.
  • silane coupling agent examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, and N- ⁇ -aminoethyl- ⁇ -.
  • Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane; ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropyltri Isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane, ⁇ -isocyanatemethyltrimethoxysilane, ⁇ -isocyanatemethyldimethoxymethylsilane; ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, Examples thereof include mercapto group-containing silanes such as ⁇ -mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as ⁇ -glycidoxypropy
  • the above adhesive-imparting agent may be used alone or in combination of two or more. Reactants of various silane coupling agents can also be used.
  • the amount of the adhesive-imparting agent used is preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). More preferably, 0.5 to 10 parts by weight.
  • a sagging inhibitor may be added to the curable composition in order to prevent sagging and improve workability.
  • the sagging inhibitor is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sauce agents may be used alone or in combination of two or more.
  • the amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B).
  • Antioxidants can be used in the curable composition.
  • the use of antioxidants can enhance the weather resistance of the cured product.
  • examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.
  • the amount of the antioxidant used is preferably 0.1 to 10 parts by weight, preferably 0, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). .2 to 5 parts by weight is more preferable.
  • a light stabilizer can be used for the curable composition.
  • the use of a light stabilizer can prevent photooxidation deterioration of the cured product.
  • Examples of the light stabilizer include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds, but hindered amine-based compounds are particularly preferable.
  • the amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, preferably 0, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). .2 to 5 parts by weight is more preferable.
  • UV absorber can be used for the curable composition.
  • the use of UV absorbers can enhance the surface weather resistance of the cured product.
  • examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted trill-based and metal chelate-based compounds, but benzotriazole-based compounds are particularly preferable, and commercially available names such as tinubin P, tinubin 213, tinubin 234 and tinubin 326, Examples thereof include chinubin 327, chinubin 328, chinubin 329, and chinubin 571 (all manufactured by BASF).
  • the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, preferably 0, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). .2 to 5 parts by weight is more preferable.
  • a tackifier resin can be added to the curable composition for the purpose of enhancing the adhesiveness and adhesion to the substrate, or if necessary.
  • the tackifier resin is not particularly limited, and a commonly used resin can be used.
  • terpen-based resins aromatic-modified terpene resins, hydrocarbon-modified terpene resins, terpen-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, kumaron inden resins, and rosin-based resins.
  • the amount of the tackifier resin used is preferably 2 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). By weight is more preferred, and 5 to 30 parts by weight is even more preferred.
  • the curable composition according to the present embodiment contains a polyoxyalkylene polymer (A), a (meth) acrylic acid ester polymer (B), an epoxy resin curing agent (D), and other additives as the agent A. Is blended, and the epoxy resin (C) and other additives are blended as the agent B, and the agent A and the agent B are preferably mixed before use to prepare a two-component type.
  • the plasticizer (E) may be blended with either or both of Agent A and Agent B.
  • the agent B contains a silanol condensation catalyst (F) and / or water (G). ) May be added.
  • the curable composition according to the present embodiment may be cured at room temperature or may be heat-cured.
  • thermal strain due to the difference in linear expansion coefficient of the dissimilar materials may become a problem, especially when heat-curing.
  • reaction-curable adhesives such as epoxy-based compositions and urethane-based compositions having high rigidity obtain high adhesive strength when heat-cured, and greatly decrease in flexibility, resulting in thermal strain when cooled. May occur.
  • the curable composition according to the present embodiment is rubber-like with a Young's modulus of several MPa to several tens of MPa even when heat-cured to such an extent that high adhesive strength can be obtained, and the occurrence of thermal strain is suppressed. Can be done.
  • high rigidity can be exhibited by subsequent room temperature curing, it is possible to produce a highly rigid adhesive that does not generate thermal strain.
  • the cured product obtained by curing the curable composition according to the present embodiment preferably has a Young's modulus of 90 MPa or more, preferably 200 MPa or more, at 23 ° C. from the viewpoint of achieving both high rigidity and flexibility. More preferred. Further, the elongation at break at 23 ° C. is preferably 70% or more, and more preferably 80% or more.
  • the method for measuring Young's modulus and elongation at break is as described in the section of Examples.
  • the curable composition according to the present embodiment can exhibit good adhesiveness to various adherends such as plastics, metals, and composite materials.
  • adherends such as plastics, metals, and composite materials.
  • non-polar materials such as polypropylene and engineering plastics having rigid molecular chains such as polyphenylene sulfide
  • the adherend can be surface-treated in advance by a known method.
  • surface treatment techniques such as sanding treatment, frame treatment, corona discharge, arc discharge, and plasma treatment can be used. Plasma treatment is preferable because it causes less damage to the adherend and stable adhesiveness can be obtained.
  • These surface treatments are also effective for removing the mold release agent used during molding and remaining on the surface of the adherend.
  • the curable composition according to the present embodiment exhibits the final desired physical properties by performing a long-term curing (curing) step after joining the adherends, but after joining the adherends. It is preferable to carry out a long-term curing (curing) step after obtaining a semi-cured product by subjecting the curable composition before curing to a relatively short-time heating step.
  • the curable composition according to the present embodiment can be suitably used as a structural adhesive for joining adherends in a continuously implemented line production method.
  • the conditions in the short-time heating step described above are not particularly limited, and examples thereof include a temperature of 50 to 200 ° C. and a time of 1 minute to 1 hour.
  • the conditions of the long-term curing (curing) step for the curable composition to exhibit the final desired physical properties, which is carried out after the short-time heating step are not particularly limited, but for example, the temperature is 5 to 5 to. Examples of the time are 50 ° C. and 24 hours to 1 week.
  • the curable composition according to the present embodiment is suitable for use as an adhesive composition, and can be used as a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, an adhesive, a waterproof material, and the like.
  • the cured product obtained by curing the curable composition has flexibility in spite of its high rigidity, and among the above-mentioned applications, it is more preferable to use it as an adhesive, particularly a structural adhesive.
  • an adhesive particularly a structural adhesive.
  • dissimilar materials such as aluminum-steel and aluminum-composite
  • the linear expansion coefficients of the two are different, so that thermal strain occurs due to temperature changes.
  • the curable composition can be suitably used for joining the dissimilar materials.
  • a sealer a polymer having a reactive silicon group as shown in the present application can be used.
  • Curable compositions are used in automobile parts such as vehicle panels, large vehicle parts such as trucks and buses, train vehicle parts, aircraft parts, marine parts, electrical parts, and various mechanical parts. It is preferably used as an adhesive.
  • the number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
  • Liquid transfer system Tosoh HLC-8120GPC Column: Tosoh TSK-GEL H type Solvent: THF Molecular weight: Polystyrene conversion Measurement temperature: 40 ° C
  • the hydroxyl value is determined by the measuring method of JIS K 1557, and the iodine value is determined by the measuring method of JIS K 0070, and the structure of the organic polymer (the degree of branching determined by the polymerization initiator used) is determined. It is the molecular weight obtained in consideration.
  • the average number of carbon-carbon unsaturated bonds introduced per terminal of the polymer (Q) shown in the examples was calculated by the following formula.
  • (Average number of introductions) [Unsaturated group concentration (mol / g) of polymer (Q) determined from iodine value-Unsaturated group concentration (mol / g) of precursor polymer (P) determined from iodine value] / [The hydroxyl group concentration (mol / g) of the precursor polymer (P) determined from the hydroxyl value].
  • the average number of silyl groups introduced per terminal of the polymer (A) shown in the examples was calculated by NMR measurement.
  • the total amount of triamine used during the polymerization was 0.15 parts by weight.
  • the monomer conversion rate polymerization reaction rate
  • the volatile matter was devolatile under reduced pressure to remove it, and a polymer concentrate was obtained.
  • the above concentrate is diluted with toluene, a filtration aid, an adsorbent (Kyoward 700SEN: manufactured by Kyowa Chemical Industry Co., Ltd.), and hydrotalcite (Kyowa Chemical Industry Co., Ltd.) are added, and the mixture is heated and stirred at about 80 to 100 ° C. After that, the solid component was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a crude polymer product.
  • a crude polymer product, 1.98 parts by weight of potassium acrylate, 100 ppm by weight of 4-hydroxy-TEMPO, and 100 parts by weight of dimethylacetamide as a solvent were added, and the mixture was reacted at 70 ° C. for 3 hours, and then the solvent was distilled off under reduced pressure to obtain the polymer.
  • a concentrate was obtained. The concentrate was diluted with toluene and the solid components were filtered off. The filtrate was concentrated under reduced pressure to obtain a macromonomer (b2-1) having an acryloyl group at one end, having a number average molecular weight of 10,500 (GPC molecular weight) and a molecular weight distribution (Mw / Mn) of 1.18.
  • Example 1 42 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 and the reactive silicon group-containing (meth) acrylic acid ester-based polymer (B) obtained in Synthesis Example 3. -1) was mixed so that the solid content was 28 parts by weight, and then isobutanol was thermally devolatile. 7 parts by weight of Ancamine K54 (manufactured by 2,4,6-tris (dimethylaminomethyl) phenol ebonic) as an epoxy resin curing agent (D) and Mesamol (manufactured by Alkylsulfonic acid phenyl ester Lanxess) as a plasticizing agent (E) in the obtained mixture.
  • Ancamine K54 manufactured by 2,4,6-tris (dimethylaminomethyl) phenol ebonic
  • D epoxy resin curing agent
  • Mesamol manufactured by Alkylsulfonic acid phenyl ester Lanxess
  • KBM-603 N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.
  • AEROSIL R-202 a filler.
  • Agent B 36 parts by weight of jER828 (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd.) as epoxy resin (C), 4 parts by weight of Silohobic 200 (hydrophobic colloidal silica Fuji Silicia Chemical Co., Ltd.) as filler, and AEROSIL R -202 (hydrophobic fumed silica manufactured by Nippon Aerosil Co., Ltd.) 1 part by weight, Neostan U-810 (dioctyl tin dilaurate manufactured by Nitto Kasei Co., Ltd.) as a silanol condensation catalyst (F) 0.3 parts by weight, water 0. A mixture of 5 parts by weight was designated as Agent B.
  • jER828 bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd.
  • Silohobic 200 hydrophobic colloidal silica Fuji Silicia Chemical Co., Ltd.
  • AEROSIL R -202 hydrophobic fumed silica manufactured by Nippon Aerosil Co.,
  • Example 2-15 and Comparative Example 1-5) A composition was prepared in the same manner as in Example 1 except that the formulation was changed to that shown in Table 1 or 2, and the viscosity and dumbbell tensile physical properties were evaluated. The results are shown in Tables 1 and 2.
  • Example 1-15 containing the plasticizer (E) selected from the group, the viscosity before curing was lower than that of Comparative Example 1 not containing the plasticizer, while 200 MPa or more after curing. It shows the young rate of ester, and it can be seen that it expresses high rigidity.
  • Examples 2, 4, 11, and 13 containing benzoic acid ester, trimellitic acid ester, or epoxidized oil and fat have a complex elastic modulus at 80 ° C. as compared with Comparative Example 2 containing diisononyl phthalate. It turns out that is high.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Une composition durcissable à composants multiples selon la présente invention comprend : un composant A contenant (A) un polymère de polyoxyalkylène ayant un groupe silicium réactif, (B) un polymère d'ester (méth)acrylate ayant un groupe silicium réactif, et (D) un agent de durcissement de résine époxy ayant une amine tertiaire ; et un composant B contenant (C) une résine époxy. Le composant A et/ou le composant B contiennent au moins un type de plastifiant (E) choisi dans le groupe constitué par les esters de sulfonate, des esters de benzoate, des esters d'éther de carboxylate aliphatique, des polyesters d'acide dibasique, des esters de trimellitate, des graisses et des huiles époxydées, ainsi que des hydrocarbures liquides aromatiques en C9.
PCT/JP2020/034007 2019-09-25 2020-09-08 Composition durcissable WO2021059972A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021548771A JPWO2021059972A1 (fr) 2019-09-25 2020-09-08

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019173868 2019-09-25
JP2019-173868 2019-09-25

Publications (1)

Publication Number Publication Date
WO2021059972A1 true WO2021059972A1 (fr) 2021-04-01

Family

ID=75166650

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/034007 WO2021059972A1 (fr) 2019-09-25 2020-09-08 Composition durcissable

Country Status (2)

Country Link
JP (1) JPWO2021059972A1 (fr)
WO (1) WO2021059972A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3929260A4 (fr) * 2019-02-18 2022-11-16 Kaneka Corporation Composition durcissable
WO2023282172A1 (fr) * 2021-07-09 2023-01-12 株式会社カネカ Composition durcissable à composants multiples
WO2023013487A1 (fr) * 2021-08-05 2023-02-09 株式会社カネカ Composition durcissable multicomposant et son utilisation
WO2023090255A1 (fr) * 2021-11-18 2023-05-25 株式会社カネカ Composition durcissable de type multi-composants

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007040101A1 (fr) * 2005-09-30 2007-04-12 Kaneka Corporation Composition pouvant etre durcie amelioree dans sa capacite de durcissement et dans sa stabilite au stockage
JP2013060589A (ja) * 2011-08-25 2013-04-04 Cemedine Co Ltd 常温湿気硬化性接着剤組成物
WO2017057719A1 (fr) * 2015-10-02 2017-04-06 株式会社カネカ Composition durcissable
US20170218223A1 (en) * 2014-08-01 2017-08-03 3M Innovative Properties Company Self sealing permeable air barrier compositions
WO2019069866A1 (fr) * 2017-10-06 2019-04-11 株式会社カネカ Composition durcissable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007040101A1 (fr) * 2005-09-30 2007-04-12 Kaneka Corporation Composition pouvant etre durcie amelioree dans sa capacite de durcissement et dans sa stabilite au stockage
JP2013060589A (ja) * 2011-08-25 2013-04-04 Cemedine Co Ltd 常温湿気硬化性接着剤組成物
US20170218223A1 (en) * 2014-08-01 2017-08-03 3M Innovative Properties Company Self sealing permeable air barrier compositions
WO2017057719A1 (fr) * 2015-10-02 2017-04-06 株式会社カネカ Composition durcissable
WO2019069866A1 (fr) * 2017-10-06 2019-04-11 株式会社カネカ Composition durcissable

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3929260A4 (fr) * 2019-02-18 2022-11-16 Kaneka Corporation Composition durcissable
WO2023282172A1 (fr) * 2021-07-09 2023-01-12 株式会社カネカ Composition durcissable à composants multiples
WO2023013487A1 (fr) * 2021-08-05 2023-02-09 株式会社カネカ Composition durcissable multicomposant et son utilisation
WO2023090255A1 (fr) * 2021-11-18 2023-05-25 株式会社カネカ Composition durcissable de type multi-composants

Also Published As

Publication number Publication date
JPWO2021059972A1 (fr) 2021-04-01

Similar Documents

Publication Publication Date Title
WO2021059972A1 (fr) Composition durcissable
JP7246313B2 (ja) 硬化性組成物
WO2021024817A1 (fr) Composition durcissable
JP7261787B2 (ja) 硬化性組成物
US20230144994A1 (en) (meth)acrylic ester copolymer and curable composition containing the same
WO2022203065A1 (fr) Composition durcissable et produit durci à base de celle-ci
US20210363347A1 (en) Curable composition
JP7341780B2 (ja) 硬化性組成物
JP7224131B2 (ja) 硬化性組成物
JP7404105B2 (ja) 硬化性組成物
WO2022163563A1 (fr) Polymère à base de polyoxyalkylène et mélange de celui-ci
JP2023010631A (ja) 多液型硬化性組成物
WO2023132323A1 (fr) Composition durcissable, et article durci associé
WO2023090255A1 (fr) Composition durcissable de type multi-composants
JP2012172111A (ja) 視認性が改良されたｆｐｄ貼り合わせ用硬化性組成物
WO2023145711A1 (fr) Composition durcissable et son utilisation
WO2023162664A1 (fr) Composition durcissable et son utilisation
WO2022203064A1 (fr) Copolymère à base d'ester d'acide (méth)acrylique et composition durcissable
WO2023282172A1 (fr) Composition durcissable à composants multiples
WO2023132324A1 (fr) Composition durcissable, et article durci associé
JP2023100363A (ja) 硬化性組成物及びその硬化物
JP2023138378A (ja) 硬化性組成物
JP2023100590A (ja) 硬化性組成物及びその硬化物
JP2023100591A (ja) 硬化性組成物及びその硬化物
WO2022186123A1 (fr) Composition durcissable

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20868800

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021548771

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20868800

Country of ref document: EP

Kind code of ref document: A1