Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/42—Introducing metal atoms or metal-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

• the present invention relates to a curable composition containing a reactive silicon group-containing (meth)acrylic acid ester polymer.
• Polymers containing reactive silicon groups are known as moisture-reactive polymers and are found in many industrial products, such as adhesives, sealants, coatings, paints, and pressure sensitive adhesives, and are used in a wide range of fields.
• the polymer components of such reactive silicon group-containing polymers are known to have a main chain structure consisting of various polymers such as polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester copolymers.
• Polymers with reactive silicon groups are stable over the long term, even when coexisting with moisture in the absence of a curing catalyst, as the silicon groups do not react, and when a curing catalyst is mixed in, the curing reaction begins from that point on.
• Tin catalysts are often used as curing catalysts, but catalysts other than tin are sometimes required.
• titanium catalysts have been developed as catalysts other than tin (see Patent Documents 1 and 2).
• the object of the present invention is to provide a curable composition that has good curability and improved storage stability without using a tin catalyst.
• the present invention relates to a compound represented by the general formula (1): -Si(R 1 ) 3-a X a (1)
• Each R1 independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group.
• Each X independently represents a hydroxyl group or a hydrolyzable group.
• a is 1, 2, or 3.
• the polymer (A) contains a reactive silicon group-containing (meth)acrylic acid ester polymer having a reactive silicon group represented by the formula:
• R2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms.
• n is an integer from 1 to 4.
• A is a ⁇ -diketone group.
• ammonium hydroxide (C) or a reaction product of the titanium compound (B) and the ammonium hydroxide (C).
• the present invention can provide a curable composition that has good curability and improved storage stability without using a tin catalyst.
• the curable composition according to the present disclosure contains a reactive silicon group-containing (meth)acrylic acid ester polymer (A) (hereinafter also referred to as polymer (A)).
• the reactive silicon group-containing polyoxyalkylene polymer (A) is represented by the general formula (1): -Si(R 1 ) 3-a X a (1) (Each R 1 independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3.)
• the compound has a reactive silicon group represented by the following formula:
• R1 is a hydrocarbon group having 1 to 20 carbon atoms.
• the number of carbon atoms in the hydrocarbon group represented by R1 is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4.
• the hydrocarbon group may be an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent.
• the hetero-containing group that the hydrocarbon group represented by R1 may have as a substituent is a group containing a hetero atom, where the hetero atom is an atom other than carbon and hydrogen atoms.
• heteroatoms include N, O, S, P, Si, and halogen atoms.
• the total number of carbon atoms and heteroatoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
• hetero-containing groups include hydroxyl groups; mercapto groups; halogen atoms such as Cl, Br, I, and F; nitro groups; cyano groups; alkoxy groups such as methoxy groups, ethoxy groups, n-propyloxy groups, and isopropyloxy groups; alkylthio groups such as methylthio groups, ethylthio groups, n-propylthio groups, and isopropylthio groups; acyl groups such as acetyl groups, propionyl groups, and butanoyl groups; acyloxy groups such as acetyloxy groups, propionyloxy groups, and butanoyloxy groups; substituted or unsubstituted amino groups such as amino groups, methylamino groups, ethylamino groups, dimethylamino groups, and diethylamino groups; substituted or unsubstituted aminocarbonyl groups such as aminocarbonyl groups, methyla
• R 1 is a hydrocarbon group substituted with a hetero-containing group
• the total number of carbon atoms and heteroatoms in R 1 is preferably 2 to 30, more preferably 2 to 18, even more preferably 2 to 10, and particularly preferably 2 to 6.
• hydrocarbon group having 1 to 20 carbon atoms as R 1 include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, and n-icosyl; vinyl.
• alkyl groups such as methyl, ethyl, n-propyl, isopropyl
• alkenyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as phenyl, naphthalene-1-yl, naphthalene-2-yl, o-phenylphenyl, m-phenylphenyl, and p-phenylphenyl; and aralkyl groups such as benzyl, phenethyl, naphthalene-1-ylmethyl, and naphthalene-2-ylmethyl.
• R 1 examples include alkyl groups such as methyl and ethyl groups, alkyl groups having a hetero-containing group such as chloromethyl and methoxymethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, etc.
• R 1 is preferably a methyl group, a methoxymethyl group, or a chloromethyl group, more preferably a methyl group or a methoxymethyl group, and even more preferably a methyl group.
• a is 1, 2, or 3. a is preferably 2 or 3, and more preferably 2 from the viewpoint of the curability of the curable composition and the productivity of the polymer (A).
• X may be, for example, a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, or an alkenyloxy group.
• an alkoxy group is more preferred because it is mildly hydrolyzable and easy to handle.
• the fewer the carbon atoms in an alkoxy group the higher the reactivity. That is, the lower the reactivity is in the order of methoxy, ethoxy, and propoxy.
• the specific structure of the reactive silicon group can be appropriately determined depending on the manufacturing method and application of the (meth)acrylic acid ester polymer (A).
• reactive silicon groups include dimethoxysilyl, trimethoxysilyl, diethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, and diisopropoxymethylsilyl.
• the dimethoxymethylsilyl, diethoxymethylsilyl, trimethoxysilyl, and triethoxysilyl groups are preferred, with the dimethoxymethylsilyl group being particularly preferred.
• the average number of reactive silicon groups contained in one molecule of the (meth)acrylic acid ester polymer (A) is preferably in the range of 0.05 to 10, more preferably in the range of 0.5 to 5, and particularly preferably in the range of 1 to 3, from the viewpoint of performance such as adhesiveness and tensile properties of the cured product.
• the position of the reactive silicon group contained in the (meth)acrylic acid ester polymer (A) is not particularly limited, and may be any of the side chain, main chain end, and/or region near the end of the polymer.
• the reactive silicon group-containing (meth)acrylic acid ester polymer (A) is a polymer having a structural unit derived from a (meth)acrylic acid ester monomer and a reactive silicon group.
• the polymer (A) can be obtained, for example, by polymerizing a monomer mixture containing a (meth)acrylic monomer and a vinyl monomer having a reactive silicon group.
• (meth)acrylic means acrylic and/or methacrylic.
• the (meth)acrylic monomer is a monomer having a (meth)acryloyl group in the molecule, and a representative example is an alkyl (meth)acrylate ester.
• the (meth)acrylic monomer may also contain the above-mentioned vinyl monomer having a reactive silicon group.
• the amount of (meth)acrylic monomer used is preferably in the range of 10 to 100% by weight, more preferably in the range of 30 to 100% by weight, and even more preferably in the range of 50 to 100% by weight, based on the total constituent monomers of the reactive silicon group-containing (meth)acrylic acid ester polymer (A).
• (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, and ) isononyl acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (
• Monomers other than (meth)acrylic acid alkyl esters include, for example, functional group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, and ethylene oxide adducts of (meth)acrylic acid; aromatic (meth)acrylic esters such as phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 2-methoxyethyl (meth)acrylate; p) Alkoxyalkyl (meth)acrylates such as 3-methoxypropyl acrylate; trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethy
• Examples of the monomer include, but are not limited to, maleimide compounds such as cyclohexylmaleimide, hexylmaleimide, octylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. One or more of these may be used.
• maleimide compounds such as cyclohexylmaleimide, hexylmaleimide, octylmaleimide, phenylmaleimide,
• the number average molecular weight (Mn) of the reactive silicon group-containing (meth)acrylic acid ester polymer (A) is preferably in the range of 2,000 to 80,000, more preferably 8,000 to 60,000, as determined by gel permeation chromatography (hereinafter also referred to as "GPC") in terms of polystyrene. If Mn is 2,000 or more, the weather resistance of the resulting cured product tends to be good, and if it is 80,000 or less, the workability of the curable composition tends to be good.
• the viscosity of the reactive silicon group-containing (meth)acrylic acid ester polymer (A) at 25°C is preferably in the range of 0.5 to 1,000 Pa ⁇ s, more preferably in the range of 5 to 800 Pa ⁇ s, and even more preferably in the range of 20 to 500 Pa ⁇ s.
• a viscosity of 0.5 Pa ⁇ s or more is preferred because it helps to prevent dripping when applied to a vertical surface, and a viscosity of 1,000 Pa ⁇ s or less tends to improve the workability of the curable composition.
• the reactive silicon group-containing (meth)acrylic acid ester polymer (A) can be produced by normal radical polymerization.
• any method such as solution polymerization, bulk polymerization, dispersion polymerization, high-temperature continuous polymerization, etc. may be adopted, and the living radical polymerization method developed in recent years may also be used.
• the reaction process may be any method such as batch, semi-batch, or continuous polymerization.
• the living radical polymerization method is preferred.
• the high-temperature continuous polymerization method may be performed according to known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, etc.
• a pressurizable reactor is filled with a solvent, and a predetermined temperature is set under pressure, and then a monomer mixture consisting of each monomer and, if necessary, a polymerization solvent is fed to the reactor at a constant feed rate, and an amount of polymerization liquid corresponding to the amount of monomer mixture fed is extracted.
• a polymerization initiator may also be mixed into the monomer mixture as necessary. When a polymerization initiator is mixed, the amount is preferably 0.001 to 2 parts by weight per 100 parts by weight of the monomer mixture.
• the pressure depends on the reaction temperature and the boiling points of the monomer mixture and solvent used, and may be any pressure that does not affect the reaction but can maintain the reaction temperature.
• the residence time of the monomer mixture is preferably 1 to 60 minutes. If the residence time is less than 1 minute, the monomers may not react sufficiently, and if the residence time exceeds 60 minutes, productivity may decrease.
• the preferred residence time is 2 to 40 minutes.
• RAFT reversible addition-fragmentation chain transfer polymerization
• NMP nitroxy radical
• ATRP atom transfer radical polymerization
• TRP polymerization using an organotellurium compound
• SBRP organoantimony compound
• BIRP organobismuth compound
• iodine transfer polymerization reversible transfer catalyzed polymerization (RTCP) using an organic catalyst
• RCMP reversible coordination mediated polymerization
• the RAFT, NMP, and ATRP methods are preferred from the viewpoints of polymerization controllability and ease of implementation.
• RAFT agent a specific polymerization control agent
• RAFT agent a specific polymerization control agent
• RAFT agent various known RAFT agents such as dithioester compounds, xanthate compounds, trithiocarbonate compounds, and dithiocarbamate compounds can be used.
• the RAFT agent may be monofunctional, having only one active site, or may be bifunctional or higher.
• the amount of RAFT agent used may be adjusted as appropriate depending on the type of monomer and RAFT agent used.
• radical polymerization initiators such as azo compounds, organic peroxides, and persulfates can be used, but azo compounds are preferred because they are safe and easy to handle and are less likely to cause side reactions during radical polymerization.
• azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), etc.
• the radical polymerization initiator may be used alone or in combination of two or more types.
• the proportion of the radical polymerization initiator used is not particularly limited, but from the viewpoint of obtaining a polymer with a narrower molecular weight distribution, it is preferable to set the amount of radical polymerization initiator used per 1 mol of RAFT agent to 0.5 mol or less, and more preferably 0.2 mol or less. Furthermore, from the viewpoint of stably carrying out the polymerization reaction, it is preferable that the lower limit of the amount of radical polymerization initiator used per 1 mol of RAFT agent is 0.01 mol.
• the amount of radical polymerization initiator used per 1 mol of RAFT agent is preferably in the range of 0.01 mol or more and 0.5 mol or less, and more preferably in the range of 0.05 mol or more and 0.2 mol or less.
• the reaction temperature during the polymerization reaction by the RAFT method is preferably 40°C or higher and 100°C or lower, more preferably 45°C or higher and 90°C or lower, and even more preferably 50°C or higher and 80°C or lower. If the reaction temperature is 40°C or higher, the polymerization reaction can proceed smoothly. On the other hand, if the reaction temperature is 100°C or lower, side reactions can be suppressed and restrictions on the initiators and solvents that can be used can be relaxed.
• a specific alkoxyamine compound having a nitroxide is used as a living radical polymerization initiator, and polymerization proceeds via the nitroxide radical derived from this.
• a nitroxide compound represented by the following general formula (4) is preferable to use.
• R 8 is an alkyl group having 1 to 2 carbon atoms or a hydrogen atom
• R 9 is an alkyl group having 1 to 2 carbon atoms or a nitrile group
• R 10 is --(CH 2 ) m --, m is 0 to 2
• R 11 and R 12 are alkyl groups having 1 to 4 carbon atoms.
• the nitroxide compound represented by the general formula (4) undergoes primary dissociation when heated to about 70 to 80°C, and undergoes an addition reaction with a vinyl monomer. At this time, it is possible to obtain a polyfunctional polymerization precursor by adding a nitroxide compound to a vinyl monomer having two or more vinyl groups. Next, the above polymerization precursor is secondarily dissociated under heating, whereby the vinyl monomer can be subjected to living polymerization.
• nitroxide compound used is adjusted appropriately depending on the type of monomer and nitroxide compound used, etc.
• polymerization may be carried out by adding 0.001 to 0.2 mol of a nitroxide radical represented by the following general formula (5) to 1 mol of the nitroxide compound represented by the above general formula (4).
• R 11 and R 12 are alkyl groups having 1 to 4 carbon atoms.
• the time required for the concentration of the nitroxide radical to reach a steady state is shortened. This makes it possible to more precisely control the polymerization, and a polymer with a narrower molecular weight distribution can be obtained.
• the amount of the nitroxide radical added is too large, the polymerization may not proceed.
• the amount of the nitroxide radical added per mol of the nitroxide compound is more preferably in the range of 0.01 to 0.5 mol, and even more preferably in the range of 0.05 to 0.2 mol.
• the reaction temperature in the NMP method is preferably 50°C or higher and 140°C or lower, more preferably 60°C or higher and 130°C or lower, even more preferably 70°C or higher and 120°C or lower, and particularly preferably 80°C or higher and 120°C or lower. If the reaction temperature is 50°C or higher, the polymerization reaction can proceed smoothly. On the other hand, if the reaction temperature is 140°C or lower, side reactions such as radical chain transfer tend to be suppressed.
• organic molecules with chain transfer ability are used as catalysts.
• the central elements of the catalyst include phosphorus, nitrogen, oxygen, and carbon.
• the catalyst is a compound with iodine bonded to the central element, for example, N-succinimide (NIS) with iodine bonded to nitrogen.
• NIS N-succinimide
• organic molecules such as tertiary amines that coordinate with the iodine of the protecting group are used as catalysts.
• the organic molecules coordinate with the iodine of dormant species and extract iodine from the dormant species (acting as an activator), reversibly generating growing radicals and complexes of iodine and the catalyst.
• Catalysts include neutral molecules such as tertiary amines and organic salts such as quaternary ammonium salts and quaternary phosphonium salts. For example, they are disclosed in the Journal of Polymers Vol. 72, No. 5 (2015).
• a method for producing a (meth)acrylic acid ester polymer having a reactive silicon group using this polymerization method is disclosed in JP-A-2022-075627 and JP-A-2022-075628.
• the "atom transfer radical polymerization method” which polymerizes (meth)acrylic acid ester monomers using organic halides or sulfonyl halide compounds as initiators and transition metal complexes as catalysts, is even more preferable as a method for producing (meth)acrylic acid ester polymers having specific functional groups, since in addition to the characteristics of the living radical polymerization method described above, it has halogens at the ends that are relatively advantageous for functional group conversion reactions, and has a large degree of freedom in the design of initiators and catalysts.
• This ATRP method is described, for example, in Matyjaszewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.), 1995, Vol. 117, p. 5614, etc.
• a polymerization reaction is generally carried out using an organic halide as an initiator and a transition metal complex as a catalyst.
• the organic halide initiator may be monofunctional or bifunctional or higher.
• the preferred types of halogen are bromides and chlorides.
• JP-A-9-272714 discloses a manufacturing method using atom transfer radical polymerization, but the present invention is not limited to this.
• a known method may be used to introduce a reactive silicon group into the main chain of the (meth)acrylic acid ester polymer (A).
• a (meth)acrylic acid ester polymer having a reactive silicon group in a side chain can be easily obtained by copolymerizing a (meth)acrylic monomer with a vinyl monomer having a reactive silicon group.
• the vinyl monomer having a reactive silicon group a compound having a reactive silicon group and a polymerizable unsaturated group in the molecule can be used.
• vinyl monomers having reactive silicon groups include reactive silicon group-containing vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane; reactive silicon group-containing (meth)acrylic acid esters such as trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, dimethylmethoxysilylpropyl (meth)acrylate, and methyldimethoxysilylpropyl (meth)acrylate; reactive silicon group-containing vinyl ethers such as trimethoxysilylpropyl vinyl ether; and reactive silicon group-containing vinyl esters such as vinyl trimethoxysilylundecanoate. One or more of these can be used.
• reactive silicon group-containing vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmeth
• the (meth)acrylic acid ester polymer containing reactive silicon groups may be produced by copolymerizing the above-mentioned monomers with other monomers that are copolymerizable with them.
• a halogen compound having a reactive silicon group (or a functional group that can be converted to a reactive silicon group) is used as an initiator for the ATRP method, it is possible to obtain a polymer having a reactive silicon group (or a functional group that can be converted to a reactive silicon group) at the polymer end on the polymerization initiation side.
• a halogen group is generally present at the polymer growth end.
• This halogen group can also be converted to a functional group having a reactive silicon group using a conventional method.
• the position of the reactive silicon group can be freely controlled according to the purpose, such as at the main chain terminal, near the terminal, or in the side chain of the polymer.
• ARGET Electron Transfer
• This method uses a reducing agent to reduce highly oxidized transition metal complexes that cause polymerization delays or termination, allowing the polymerization reaction to proceed quickly to a high reaction rate even under low catalyst conditions with a small amount of transition metal complex.
• This ARGET method can also be used to produce polymer (A).
• the curable composition according to one embodiment of the present disclosure may contain a titanium compound (B) represented by general formula (2).
• R 2 -O) n Ti-A 4-n (2) R2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 4.
• A is a ⁇ -diketone group.
• the substituted or unsubstituted hydrocarbon group represented by R 2 is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, more preferably an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include saturated or unsaturated hydrocarbon groups.
• Examples of the saturated hydrocarbon group include linear or branched alkyl groups.
• the number of carbon atoms in the hydrocarbon group is 1 to 10, preferably 1 to 6, and more preferably 1 to 4.
• Examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl.
• Examples of the substituent that the hydrocarbon group may have include a methoxy group, an ethoxy group, a hydroxyl group, and an acetoxy group. When a plurality of R 2s are present, they may be the same as or different from each other.
• the ⁇ -diketone group represented by A is not particularly limited as long as it is a ⁇ -diketone that can be blended with titanium, but examples thereof include 1-aryl-1,3-butanedione such as 2,4-pentanedione, 2,4-hexanedione, 2,4-pentadecanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-phenyl-1,3-butanedione, 1-(4-methoxyphenyl)-1,3-butanedione, 1,3-diaryl-1,3-propanedione, 1,3-bis(2-pyridyl)-1,3-propanedione, and 1,3-bis(4-methoxyphenyl)-1,3-propanedione.
• 1-aryl-1,3-butanedione such as 2,4-pentanedione, 2,4-hexanedione, 2,
• diketones examples include 1,3-propanedione and 3-benzyl-2,4-pentanedione, ketoesters such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate and ethyl 3-oxohexanoate, ketoamides such as N,N-dimethyl acetoacetamide, N,N-diethyl acetoacetamide and acetoacetanilide, malonic acid esters such as dimethyl malonate, diethyl malonate and diphenyl malonate, and malonic acid amides such as N,N,N',N'-tetramethyl malonamide and N,N,N',N'-tetraethyl malonamide.
• ketoesters such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, t-butyl
• diketones and ketoamides are preferred, and diketones are more preferred.
• 2,4-pentanedione, 1-aryl-1,3-butanedione, 1,3-diaryl-1,3-propanedione, methyl acetoacetate, and ethyl acetoacetate are preferred, and methyl acetoacetate and ethyl acetoacetate are particularly preferred.
• multiple A's may be the same or different.
• n represents an integer of 1 to 4. In order to achieve better curability, n is preferably 2, 3, or 4, and is particularly preferably 4.
• titanium compounds represented by general formula (2) include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, and diethoxydibutoxytitanium.
• titanium ester examples include titanium dioxide, titanium ethoxytriisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxydibutoxytitanium, tetrabutoxytitanium, tetra(tert-butoxy)titanium, tetra(sec-butoxy)titanium, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethyl acetoacetate), diisobutoxytitanium bis(acetylacetonate), and diisobutoxytitanium bis(ethyl acetoacetate).
• diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), diisobutoxytitanium bis(acetylacetonate), diisobutoxytitanium bis(ethylacetoacetate), tetraisopropoxytitanium, tetrabutoxytitanium, tetra(tert-butoxy)titanium, and tetra(sec-butoxy)titanium are preferred, with diisopropoxytitanium bis(ethylacetoacetate), diisobutoxytitanium bis(ethylacetoacetate), tetraisopropoxytitanium, and tetra(tert-butoxy)titanium being particularly preferred.
• the above titanium compounds (B) may be used alone or in combination of two or more.
• the amount of titanium compound (B) used is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
• the curable composition according to one embodiment of the present disclosure may include ammonium hydroxide (C).
• the ammonium hydroxide (C) is preferably represented by the following general formula (3).
• R 4 , R 5 , R 6 and R 7 are the same or different and each represents a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms.
• Y represents a hydroxyl group.
• the substituted or unsubstituted hydrocarbon groups represented by R 4 , R 5 , R 6 , and R 7 are preferably substituted or unsubstituted aliphatic or aromatic hydrocarbon groups, and more preferably aliphatic hydrocarbon groups.
• As the aliphatic hydrocarbon group a straight-chain or branched alkyl group is preferable.
• the number of carbon atoms in the hydrocarbon group is 1 to 8, preferably 1 to 6, and more preferably 1 to 4.
• saturated hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, and octyl group
• unsaturated hydrocarbon groups such as vinyl group, allyl group, prenyl group, crotyl group, and cyclopentadienyl group are exemplified, and a methyl group, an ethyl group, and a butyl group are preferable.
• aromatic hydrocarbon group examples include a phenyl group, a tolyl group, and a benzyl group.
• Substituents that the hydrocarbon group may have include methoxy, ethoxy, hydroxy, and acetoxy groups.
• Substituted hydrocarbon groups include alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups, hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, and 3-hydroxypropyl groups, and 2-acetoxyethyl groups.
• ammonium hydroxides represented by general formula (3) include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, and tris(2-hydroxyethyl)methylammonium hydroxide.
• tetraalkylammonium hydroxides are preferred, and tetrabutylammonium hydroxide is more preferred.
• the amount of ammonium hydroxide (C) used is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
• the molar ratio of the titanium compound (B) to the ammonium hydroxide (C) (B/C) is in the range of 0.1/1 to 10/1, and from the viewpoint of obtaining good curability, 1/1 to 10/1 is preferable, and 2/1 to 5/1 is even more preferable.
• the curable composition according to the present disclosure may contain both the titanium compound (B) and the ammonium hydroxide (C), or may contain a reaction product obtained by reacting the titanium compound (B) with the ammonium hydroxide (C).
• the curability is good and the storage stability can be improved, but the embodiment using the reaction product is preferred because the curability and storage stability can be improved.
• the reaction product can be obtained by reacting the mixture of the two at, for example, 40 to 100°C. Specifically, this temperature is preferably 40 to 100°C.
• the molar ratio of the titanium compound (B) to the ammonium hydroxide (C) in the mixture may be, for example, 0.1 to 100, and more preferably 0.2 to 10.
• the amount of the reaction product of the titanium compound (B) and ammonium hydroxide (C) used is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, and particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
• the curable composition according to the present disclosure may contain only the (meth)acrylic acid ester-based polymer (A) as the polymer having a reactive silicon group, or may further contain, in addition to the polymer (A), a polymer (D) other than the polymer (A) that has a reactive silicon group.
• the reactive silicon group of polymer (D) can be represented by the above-mentioned general formula (1).
• the reactive silicon group of polymer (A) and the reactive silicon group of polymer (D) may be the same silicon group or different silicon groups.
• reactive silicon groups in polymer (D) include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl.
• dimethoxymethylsilyl, trimethoxysilyl, triethoxysilyl, and (methoxymethyl)dimethoxysilyl are preferred because they give cured products with good mechanical properties.
• trimethoxysilyl groups, (chloromethyl)dimethoxysilyl groups, and (methoxymethyl)dimethoxysilyl groups are more preferred, and trimethoxysilyl groups are particularly preferred because they improve curing properties.
• polymer (D) examples include, but are not limited to, reactive silicon group-containing polyoxyalkylene polymers.
• the main chain structure of the polyoxyalkylene polymer may be linear or branched.
• the main chain of the reactive silicon group-containing polyoxyalkylene polymer is a polymer having a repeating unit represented by -R13 -O- (wherein R13 is a linear or branched alkylene group having 1 to 14 carbon atoms), and R13 is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.
• repeating unit represented by -R13- O- include -CH2O- , -CH2CH2O-, -CH2CH ( CH3) O- , -CH2C ( CH3 )( CH3 )O- and -CH2CH2CH2CH2O- , with -CH2CH2O- and -CH2CH ( CH3 )O- being preferred, and -CH2CH ( CH3 ) O- being more preferred.
• the reactive silicon group-containing polyoxyalkylene polymer can be produced by introducing a reactive silicon group into a precursor polymer to which a reactive silicon group can be introduced.
• the reactive silicon group-containing polyoxyalkylene polymer can be produced by introducing an olefin group into a polyoxyalkylene polymer (d1) having a hydroxyl group at its end, utilizing the reactivity of the hydroxyl group to obtain a precursor polymer having an olefin group, and then reacting the precursor polymer with a reactive silicon group-containing compound that is reactive with the olefin group to introduce the reactive silicon group.
• the polymer backbone of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, thereby obtaining a polyoxyalkylene polymer (d1) having a hydroxyl group at its end.
• a polymerization method using a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is preferred because it can obtain a hydroxyl-terminated polymer with a small molecular weight distribution (Mw/Mn).
• Initiators having hydroxyl groups are not particularly limited, but examples include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, butanol, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol, low molecular weight polyoxypropylene monoallyl ether, low molecular weight polyoxypropylene monoalkyl ether, etc.
• glycerin pentaerythritol, low molecular weight polyoxypropylene triol, etc., which have three or more hydroxyl groups, can be used.
• the epoxy compound is not particularly limited, but examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.
• reaction with alkali metal salts When introducing an olefin group into a polyoxyalkylene polymer (d1) having a hydroxyl group at its terminal, it is preferable to first react an alkali metal salt with the polyoxyalkylene polymer (d1) to convert the terminal hydroxyl group into a metaloxy group.
• a composite metal cyanide complex catalyst can be used instead of the alkali metal salt. In this manner, a metaloxy group-terminated polyoxyalkylene polymer (d2) is formed.
• the alkali metal salt is not particularly limited, but examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide, etc. From the viewpoints of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, and sodium methoxide and sodium tert-butoxide are more preferred. From the viewpoint of availability, sodium methoxide is preferred.
• the alkali metal salt may be dissolved in a solvent and then subjected to the reaction.
• the metaloxy group-terminated polyoxyalkylene polymer (d2) obtained as described above can be converted into a structure containing an olefin group by reacting an electrophilic agent (d3) having an olefin group, thereby forming a polyoxyalkylene polymer (d4) having an olefin group in the terminal structure.
• the electrophile (d3) having an olefin group is not particularly limited as long as it is a compound that can react with the metaloxy group of the polyoxyalkylene polymer (d2) and introduce an olefin group into the polyoxyalkylene polymer, but examples of the electrophile include an organic halide (d3-1) having an olefin group and an epoxy compound (d3-2) having an olefin group.
• An organic halide (d3-1) having an olefin group which is one embodiment of the electrophile (d3), reacts with the metaloxy group through a halogen substitution reaction to form an ether bond, thereby introducing a structure containing an olefin group as the terminal structure of the polyoxyalkylene polymer.
• organic halides (d3-1) having an olefin group include, but are not limited to, vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred for ease of handling. Furthermore, methallyl chloride, methallyl bromide, and methallyl iodide are preferred because they improve the average ratio of the number of reactive silicon groups to the number of terminals of the polymer skeleton.
• a halogenated hydrocarbon compound having a carbon-carbon triple bond can be used as the organic halide (d3-1) having an olefin group.
• the polyoxyalkylene polymer (d5) obtained by reacting this compound has a carbon-carbon triple bond at the end of the polymer backbone.
• a reactive silicon group is introduced into such a polymer (d5), the atom adjacent to the reactive silicon group has a carbon-carbon double bond.
• halogenated hydrocarbon compounds having a carbon-carbon triple bond examples include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-io
• propargyl chloride, propargyl bromide, and propargyl iodide are more preferred.
• a halogenated hydrocarbon compound having a carbon-carbon double bond may be used simultaneously with a halogenated hydrocarbon compound having a carbon-carbon triple bond.
• an epoxy compound (d3-2) having an olefin group can react with the metaloxy group through a ring-opening addition reaction of the epoxy group to form an ether bond, thereby introducing a structure containing an olefin group and a hydroxyl group as the terminal structure of the polyoxyalkylene polymer.
• a single or multiple epoxy compounds (d3-2) can be added to one metaloxy group by adjusting the amount of epoxy compound (d3-2) used relative to the metaloxy group and the reaction conditions.
• epoxy compound (d3-2) having an olefin group are not particularly limited, but allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monoxide are preferred in terms of reaction activity, with allyl glycidyl ether being particularly preferred.
• the polyoxyalkylene polymer (d4) having an olefin group in the terminal structure or the polyoxyalkylene polymer (d5) (precursor polymer) having a carbon-carbon triple bond in the terminal structure obtained as above can be subjected to a hydrosilylation reaction with a hydrosilane compound (d6) having a reactive silicon group, thereby producing a polyoxyalkylene polymer containing a reactive silicon group.
• the hydrosilylation reaction has the advantages that it can be easily carried out, the amount of reactive silicon group introduced can be easily adjusted, and the physical properties of the obtained polymer are stable.
• hydrosilane compound (d6) having a reactive silicon group include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxysilane.
• halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(
• the hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst.
• a hydrosilylation catalyst include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, and complexes thereof.
• polymer (A) As another method for producing polymer (A), a method can be applied in which a compound (d7) having a reactive silicon group and an isocyanate group in one molecule is allowed to react with a polyoxyalkylene polymer (d1) (precursor polymer) having a hydroxyl group at the end to form a urethane bond and introduce a reactive silicon group.
• Polymer (A) can also be produced by this method.
• the compound (d7) having a reactive silicon group and an isocyanate group in one molecule is not particularly limited as long as it is a compound having both an isocyanate group capable of undergoing a urethane reaction with the hydroxyl group of the polyoxyalkylene polymer (d1) and a reactive silicon group in one molecule, but specific examples include (3-isocyanatepropyl)trimethoxysilane, (3-isocyanatepropyl)dimethoxymethylsilane, (3-isocyanatepropyl)triethoxysilane, (3-isocyanatepropyl)diethoxymethylsilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)triethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, (isocyanatemethyl)diethoxymethylsilane, etc.
• the urethanization reaction may be carried out without using a urethanization catalyst, but may be carried out in the presence of a urethanization catalyst in order to improve the reaction rate or the reaction rate.
• a urethanization catalyst for example, a conventionally known urethanization catalyst such as the catalysts listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963, can be used. Specific examples include, but are not limited to, base catalysts such as organotin compounds, bismuth compounds, and organic amines.
• a method for producing a polyoxyalkylene polymer containing reactive silicon groups a method can be applied in which a polyoxyalkylene polymer (d1) having a hydroxyl group at its terminal is reacted with an excess of a polyisocyanate compound (d8) to produce a polymer (precursor polymer) having an isocyanate group at its terminal, and then the precursor polymer is reacted with a compound (d9) having a group that reacts with an isocyanate group (e.g., an amino group) and a reactive silicon group.
• This method can also be used to produce a polyoxyalkylene polymer having a reactive silicon group at the terminal of the polymer backbone.
• polyisocyanate compounds (d8) include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.
• Examples of compounds (d9) having a group that reacts with an isocyanate group and a reactive silicon group include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyldimethoxymethylsilane, ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyldimethoxymethylsilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -(N-phenyl)aminopropyltrimethoxysilane, ⁇ -(N-phenyl)aminopropyldi Examples include amino group-containing silanes such as methoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-
• a compound (d10) having a reactive silicon group and a mercaptan group in one molecule can be reacted with a polyoxyalkylene polymer (d4) (precursor polymer) having an olefin group in its terminal structure to form a sulfide bond by addition of the mercaptan group to the olefin group, thereby introducing a reactive silicon group.
• d4 polyoxyalkylene polymer having an olefin group in its terminal structure to form a sulfide bond by addition of the mercaptan group to the olefin group, thereby introducing a reactive silicon group.
• This method can also be used to produce a polyoxyalkylene polymer having a reactive silicon group at the end of the polymer backbone.
• the compound (d10) having a reactive silicon group and a mercaptan group in one molecule is not particularly limited as long as it is a compound having both a mercaptan group capable of undergoing an addition reaction with an olefin group in the polyoxyalkylene polymer (d4) and a reactive silicon group in one molecule, but specific examples include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, (mercaptomethyl)triethoxysilane, etc.
• the addition reaction of the mercaptan group to the olefin group may be carried out without using a radical initiator, but may be carried out in the presence of a radical initiator in order to improve the reaction rate or the reaction rate.
• a radical initiator a conventionally known initiator may be used. Specific examples include, but are not limited to, azo-based initiators and peroxide-based initiators.
• azo initiators such as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 2,2'-azobis(1-methylcyclohexanecarbonitrile) (V-40) are particularly preferred.
• AIBN 2,2'-azobis(isobutyronitrile)
• V-59 2,2'-azobis(2-methylbutyronitrile)
• V-40 2,2'-azobis(1-methylcyclohexanecarbonitrile)
• the content ratio of polymer (A) and polymer (D) is not particularly limited and can be set appropriately, but from the viewpoint of prioritizing the characteristics of the (meth)acrylic acid ester polymer (A) and improving the storage stability of the curable composition while maintaining good curability, it is preferable that the weight ratio of the (meth)acrylic acid ester polymer (A) is 50% or more of the total of the (meth)acrylic acid ester polymer (A) and the polymer (D).
• the weight ratio of the (meth)acrylic acid ester polymer (A) may be more than 70%, more than 80%, or more than 95%.
• the upper limit may be 100%.
• the curable composition according to the present disclosure may contain other additives such as other silanol condensation catalysts, fillers, adhesion promoters, plasticizers, solvents, diluents, sagging inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, physical property adjusters, tackifier resins, compounds containing epoxy groups, photocurable substances, oxygen curable substances, epoxy resins, and other resins.
• additives may be added to the curable composition according to the present disclosure as necessary for the purpose of adjusting the various physical properties of the curable composition or the cured product.
• additives include, for example, surface improvers, foaming agents, curability adjusters, flame retardants, silicates, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.
• a titanium compound (B) and ammonium hydroxide (C), or a reaction product thereof are used as a silanol condensation catalyst for hydrolyzing and condensing the reactive silicon groups of the polymer (A) having a reactive silicon group, but other silanol condensation catalysts may also be used in combination.
• silanol condensation catalysts include, for example, organotin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, etc.
• organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, reaction products of dibutyltin oxide with silicate compounds, reaction products of dioctyltin oxide with silicate compounds, and reaction products of dibutyltin oxide with phthalic acid esters.
• metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, calcium carboxylate, etc.
• the carboxylate group can be a combination of the following carboxylic acids with various metals.
• iron 2-ethylhexanoate (divalent), iron 2-ethylhexanoate (trivalent), titanium 2-ethylhexanoate (tetravalent), vanadium 2-ethylhexanoate (trivalent), calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent), barium 2-ethylhexanoate (divalent), manganese 2-ethylhexanoate (divalent), nickel 2-ethylhexanoate (divalent), cobalt 2-ethylhexanoate (divalent), zirconium 2-ethylhexanoate (tetravalent), iron neodecanoate (divalent), iron neodecanoate (trivalent), titanium neodecanoate (tetravalent), vanadium neodecanoate (trivalent), calcium neodecanoate
• amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.
• amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine
• nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (
• carboxylic acids 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 aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).
• silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.
• Two or more different types of silanol condensation catalysts may be used in combination.
• the amount of silanol condensation catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of polymer (A) having a reactive silicon group.
• the curable composition according to the present disclosure may contain various fillers, such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filament.
• various fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filament.
• the amount of filler used is preferably 1 to 600 parts by weight, and more preferably 10 to 300 parts by weight, per 100 parts by weight of polymer (A) having reactive silicon groups.
• organic balloons or inorganic balloons may be added.
• the balloons are spherical fillers that are hollow inside, and examples of the materials for the balloons include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran.
• the amount of the balloons used is preferably 0.1 to 100 parts by weight, and particularly preferably 1 to 20 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
• An adhesion promoter may be added to the curable composition according to the present disclosure.
• a silane coupling agent or a reaction product of a silane coupling agent can be added.
• silane coupling agents include amino group-containing silanes such as ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane, and ⁇ -isopropyltrimethoxysilane;
• silanes include isocyanate group-containing silanes such as isocyanate propyl methyl dimethoxy silane, ⁇ -isocyanate methyl trimeth
• condensation products of various silane coupling agents such as condensation products of aminosilane, condensation products of aminosilane and other alkoxysilanes, reaction products of aminosilane and epoxysilane, reaction products of aminosilane and (meth)acrylic group-containing silane, and other reaction products of various silane coupling agents can also be used.
• Specific examples include Dynasylan 1146 and Dynasylan 1124 (manufactured by EVONIK).
• the above adhesion promoters may be used alone or in combination of two or more.
• the amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
• a plasticizer can be added to the curable composition according to the present disclosure.
• the plasticizer include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; and 1,2-cyclohexanedicarboxylic acid diisononyl ester (specifically, Hexamoll, available under the trade name).
• phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthal
• non-phthalate ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters (specifically, trade name: Mesamoll (manufactured by LANXESS)); phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil, and epoxy plasticizers such as epoxy benzyl stearate.
• unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate
• polymeric plasticizers can be used.
• polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or more, and polyethers such as derivatives in which the hydroxyl groups of these polyether polyols are converted to ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc.
• the amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group. If the amount is less than 5 parts by weight, the effect of the plasticizer will not be manifested, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.
• the plasticizer may be used alone or in combination of two or more types.
• a solvent or diluent can be added to the curable composition according to the present disclosure.
• the solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc. can be used.
• the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher, in view of the problem of air pollution when the composition is used indoors.
• the above solvents or diluents may be used alone or in combination of two or more kinds.
• the curable composition according to the present disclosure may contain an anti-sagging agent as necessary to prevent sagging and improve workability.
• the anti-sagging agent is not particularly limited, and may be, for example, polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
• the amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of polymer (A) having reactive silicon groups.
• the curable composition according to the present disclosure may contain an antioxidant (anti-aging agent).
• an antioxidant can improve the weather resistance of the cured product.
• examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols.
• BHT antioxidant
• Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520, and SONGNOX 1076 are listed.
• hindered amine light stabilizers such as TINUVIN 622LD, TINUVIN 144, TINUVIN 292, CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by BASF), Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, Adeka STAB LA-68 (all manufactured by ADEKA Corporation), Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.), and Nocrac CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used.
• antioxidants such as SONGNOX 4120, Naugard 445, and OKABEST CLX050 can also be used.
• antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
• the amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of polymer (A) having a reactive silicon group.
• a light stabilizer can be used in the curable composition according to the present disclosure.
• the use of a light stabilizer can prevent photo-oxidative deterioration of the cured product.
• Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred.
• hindered amine light stabilizers include TINUVIN 123, TINUVIN 144, TINUVIN 249, TINUVIN 292, TINUVIN 312, TINUVIN 622LD, TINUVIN 765, TINUVIN 770, TINUVIN 880, TINUVIN 5866, and TINUVIN B97; CHIMASSORB 119FL and CHIMASSORB 944LD (all manufactured by BASF); Adeka STAB LA-57, LA-62, LA-63, LA-67, and LA-68 (all manufactured by ADEKA CORPORATION); Sanol LS-292, LS-2626, LS-765, LS-744, and LS-1114 (all manufactured by Sankyo Lifetech Co., Ltd.); SABOSTAB UV91 and SABOSTAB Examples of light stabilizers include UV119, SONGSORB CS5100, SONGSORB CS622, SONGSORB CS944 (all manufactured by SONGWON), and Nocrac CD (
• the amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of polymer (A) having a reactive silicon group.
• the curable composition according to the present disclosure may contain an ultraviolet absorber.
• the use of an ultraviolet absorber may improve the surface weather resistance of the cured product.
• Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, triazine-based, substituted acrylonitrile-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred.
• Examples include Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, and Tinuvin 1600 (all manufactured by BASF); and SONGSORB 3290 (manufactured by SONGWON).
• Examples of triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 477, and TINUVIN 1577ED (all manufactured by BASF), and SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON).
• Examples of benzophenone compounds include SONGSORB 8100 (manufactured by SONGWON).
• the amount of UV absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
• Addworks IBC760 (manufactured by Clariant) can also be used as a product that contains a mixture of antioxidants, light stabilizers, and UV absorbers.
• the curable composition according to the present disclosure may contain a physical property adjuster for adjusting the tensile properties of the resulting cured product as necessary.
• the physical property adjuster is not particularly limited, but examples thereof include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl
• the hardness of the curable composition according to the present disclosure when cured can be increased, or conversely, the hardness can be reduced to provide a breaking elongation.
• the physical property adjuster may be used alone or in combination of two or more kinds.
• compounds that produce compounds having monovalent silanol groups in the molecule upon hydrolysis have the effect of lowering the modulus of the cured product without increasing the stickiness of the surface of the cured product.
• Compounds that produce trimethylsilanol are particularly preferred.
• Examples of compounds that produce compounds having monovalent silanol groups in the molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and that produce silane monool upon hydrolysis. Specific examples include phenoxytrimethylsilane, tris((trimethylsiloxy)methyl)propane, etc.
• the amount of the property adjuster used is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
• a tackifier resin can be added for the purpose of increasing the adhesiveness or adhesion to the substrate, or for other reasons as required.
• a tackifier resin there are no particular limitations on the tackifier resin, and any commonly used resin can be used.
• terpene resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used alone or in combination of two or more.
• petroleum resins e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins,
• the amount of tackifier resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight, per 100 parts by weight of polymer (A) having reactive silicon groups. If it is less than 2 parts by weight, it will be difficult to achieve adhesion and adhesion to the substrate, and if it exceeds 100 parts by weight, the viscosity of the composition may become too high, making it difficult to handle.
• a compound containing an epoxy group can be used.
• the use of a compound having an epoxy group can improve the restorability of the cured product.
• the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof.
• epoxy compound is preferably used in the range of 0.5 to 50 parts by weight per 100 parts by weight of the polymer (A) having a reactive silicon group.
• a photocurable material can be used in the curable composition according to the present disclosure.
• a photocurable material When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product.
• Many compounds of this type are known, such as organic monomers, oligomers, resins, or compositions containing them.
• Representative compounds that can be used include unsaturated acrylic compounds, which are monomers, oligomers, or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, polyvinyl cinnamates, or azido resins.
• the photocurable substance should be used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having reactive silicon groups. If it is less than 0.1 part by weight, there is no effect of improving weather resistance, and if it is more than 20 parts by weight, the cured product becomes too hard and tends to crack.
• oxygen-curable substance can be used in the curable composition according to the present disclosure.
• oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which react with oxygen in the air to form a cured film near the surface of the cured product, preventing stickiness of the surface and adhesion of dirt and dust to the surface of the cured product.
• oxygen-curable substances include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and C5 to C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These may be used alone or in combination of two or more types.
• the amount of oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight per 100 parts by weight of polymer (A) having reactive silicon groups, and more preferably 0.5 to 10 parts by weight. If the amount used is less than 0.1 part by weight, the improvement in stain resistance will not be sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product will tend to be impaired. As described in JP-A-3-160053, it is recommended that oxygen-curable substances be used in combination with photocurable substances.
• the curable composition according to the present disclosure can be used in combination with an epoxy resin.
• the composition containing the epoxy resin is particularly suitable as an adhesive, particularly as an adhesive for exterior wall tiles.
• Examples of the epoxy resin include bisphenol A type epoxy resins and novolac type epoxy resins.
• a curing agent that cures the epoxy resin can be used in combination with the curable composition according to the present disclosure.
• the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used.
• the amount used is in the range of 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.
• the curable composition according to the present disclosure can be prepared as a one-component type in which all ingredients are mixed and stored in a sealed state in advance, and cured by moisture in the air after application, or as a two-component type in which ingredients such as a curing catalyst, a filler, a plasticizer, and water are mixed separately as a curing agent, and the ingredients are mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.
• the curable composition is a one-component type
• all of the ingredients are premixed, so it is preferable to dehydrate and dry ingredients that contain water before use, or to dehydrate them by reducing pressure during mixing.
• storage stability can be further improved by adding an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, or ⁇ -glycidoxypropyltrimethoxysilane.
• an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptoprop
• the amount of the dehydrating agent, particularly a silicon compound that can react with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
• the curable composition according to the present disclosure can be used as a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproofing material, a coating waterproofing material, a mold release agent, an anti-vibration material, a vibration-damping material, a sound-proofing material, a foaming material, a paint, a spraying material, etc.
• the cured product obtained by curing the curable composition according to the present disclosure has excellent flexibility and adhesiveness, and is therefore more preferably used as a sealing material or an adhesive.
• electrical and electronic component materials such as solar cell back sealing materials
• electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for equipment, acoustic insulating materials, elastic adhesives, binders, contact adhesives, spray-type sealants, crack repair materials, tiling adhesives, adhesives for asphalt waterproofing materials, powder paints, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealants, dental impression materials, food packaging materials, joint sealants for exterior materials such as sizing boards, coating materials, anti-slip coating materials, buffer materials, primers, conductive materials for electromagnetic wave shielding, thermally conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, concrete reinforcing materials, temporary adhesives, various molding materials, and liquid sealants for rust prevention and waterproofing of the edges (cut parts) of wire-reinforced glass and laminated glass, and for automobile parts, trucks, buses and other large vehicle parts
• the composition in the case of automobiles, can be used in a wide variety of applications, such as adhesive attachment of plastic covers, trims, flanges, bumpers, window attachments, interior components, exterior components, etc.
• the composition can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer, it can also be used as various types of sealing compositions and adhesive compositions.
• the curable composition according to the present disclosure can also be used as an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, an adhesive for wall finishing, an adhesive for vehicle panels, an adhesive for assembling electrical, electronic, and precision equipment, an adhesive for bonding leather, textile products, fabrics, paper, boards, and rubber, a reactive post-crosslinking pressure-sensitive adhesive, a sealant for direct glazing, a sealant for double-glazing, a sealant for SSG construction, or a sealant for working joints in buildings, and materials for civil engineering and bridge construction.
• the composition can also be used as an adhesive material, such as an adhesive tape or an adhesive sheet.
• a is 1, 2, or 3.
• the polymer (A) contains a reactive silicon group-containing (meth)acrylic acid ester polymer having a reactive silicon group represented by the formula: Furthermore, the general formula (2): (R 2 -O) n Ti-A 4-n (2) ( R2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 4. A is a ⁇ -diketone group.) and ammonium hydroxide (C), or a reaction product of the titanium compound (B) and the ammonium hydroxide (C). [Item 2] 2. The curable composition according to item 1, wherein a in general formula (1) is 2. [Item 3] 3.
• the curable composition according to any one of items 1 to 4 wherein the weight ratio of the (meth)acrylic acid ester polymer (A) is 50% or more in the total of the (meth)acrylic acid ester polymer (A) and the polymer (D).
• the number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.
• Liquid delivery system Waters e2695 Column: Showa Denko Shodex GPC K-804, K-802.5
• Solvent Chloroform Molecular weight: Polystyrene equivalent Measurement temperature: 40°C
• the average number of reactive silicon groups per polymer molecule was calculated based on the polymer structure and NMR measurement results.
• the terminal bromine groups of the polymer were reacted with 1,7-octadiene in acetonitrile solvent using a pentamethyldiethylenetriamine complex of cuprous bromide as a catalyst to obtain a polyacrylic acid ester.
• the amount of 1,7-octadiene used was 40 molar equivalents relative to the initiator.
• unreacted 1,7-octadiene was removed and recovered by volatilization.
• the resulting polymer was purified with an adsorbent, heated to about 190° C. for debromination, and purified again with an adsorbent to obtain a polyacrylic ester having alkenyl groups at both ends.
• the polyacrylic acid ester having alkenyl groups at both ends was subjected to hydrosilylation reaction with methyldimethoxysilane on the alkenyl groups of the polyacrylic acid ester using 300 ppm of an isopropanol solution of a platinum vinylsiloxane complex containing 3 wt% platinum as a catalyst.
• the reaction conditions were 100°C and 1 hour.
• the reaction was carried out in the presence of methyl orthoformate, and 2 molar equivalents of methyldimethoxysilane were used relative to the alkenyl groups.
• the unreacted methyldimethoxysilane and methyl orthoformate were removed by volatilization to obtain a polyacrylic acid ester terminated with a methyldimethoxysilyl group.
• the number average molecular weight of the obtained polymer was 25,000, the molecular weight distribution was 1.3, and the number of silyl groups introduced per molecule was 2.0.
• Example 1 To 100 parts by weight of the polymer (A-1) obtained in Synthesis Example 1, 1.0 part by weight of the catalyst (B-1) obtained in Synthesis Example 2 was added and mixed uniformly. The obtained curable composition was used to evaluate the curability and storage stability as follows, and the results are shown in Table 1.
• Polymer (A-1) was weighed into a plastic container under an atmosphere of 23°C and relative humidity of 50%, and a curing catalyst was added so as to give the composition ratio shown in Table 1, followed by thorough mixing using a foaming mixer.
• the mixture was filled into a formwork about 5 mm thick using a spatula, and the time when the surface was smoothed to a flat surface was recorded as the curing initiation time.
• the surface was touched with the spatula, and the time when the mixture no longer adhered to the spatula was recorded as the skinning time, and the curing time (curability) was measured.
• Storage stability refers to the viscosity stability after thoroughly mixing the polymer (A-1) and the curing catalyst, sealing the mixture after nitrogen gas is filled in, and the stability was quantified and evaluated by the following method.
• the water content in the polymer was adjusted to about 120 ppm in a 23°C environment, and the viscosity (initial viscosity) was measured using an E-type viscometer. After that, the mixture was left standing still in a 23°C environment for 4 weeks, and then left standing still under a temperature condition of 23°C, and the viscosity (post-storage viscosity) was measured using an E-type viscometer.
• Example 1 The same evaluation as in Example 1 was carried out except that 1.0 part by weight of the catalyst (B-1) was changed to 2.5 parts by weight of dioctyltin/laurylamine. The results are shown in Table 1.
• Example 2 The same evaluation as in Example 1 was carried out, except that 1.0 part by weight of the catalyst (B-1) was changed to 2.5 parts by weight of TIB KAT K25 (potassium neodecanoate, manufactured by TIB Chemical Co., Ltd.). The results are shown in Table 1.
• Example 1 which contained the reactive silicon group-containing (meth)acrylic acid ester polymer (A) and the reaction product of the titanium compound (B) and ammonium hydroxide (C), showed faster curing and improved storage stability compared to Comparative Examples 1 and 2, which used catalysts other than the titanium compound (B) and ammonium hydroxide (C).

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