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• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/08—Saturated oxiranes
  • C08G65/10—Saturated oxiranes characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • 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
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
• • 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
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • 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
• • C—CHEMISTRY; METALLURGY
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  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
  • C09K2200/0657—Polyethers

Definitions

• the present invention relates to a crystalline polyoxyalkylene polymer and a curable composition containing the same.
• rubber-like cured products can be obtained from polymers that have at least one reactive silicon group in the molecule. This is because the reactive silicon group is hydrolyzed by moisture, forming a crosslinked network of siloxane bonds. This reaction proceeds even at room temperature.
• Such polymer main chain structures include polyoxyalkylene, polyacrylic acid ester, polyisobutylene, etc. These polymers are already being produced industrially and are widely used in applications such as sealants, adhesives, paints, and waterproofing materials (see Patent Documents 1 to 4).
• polymers whose main chain structure is polyoxyalkylene have a wide range of applications. This is because they have a relatively low viscosity at room temperature, making them easy to handle, and the mechanical properties of the resulting cured product are good.
• One aspect of the present invention aims to provide a polyoxyalkylene polymer that can provide a cured product with excellent elastic modulus and strength, and a curable composition containing the same.
• the present inventors have conducted extensive research to solve the above problems. As a result, they have discovered that the problems can be solved by making a polyoxyalkylene polymer having a reactive silicon group into a crystalline polymer.
• the crystalline polyoxyalkylene polymer (A) has a reactive silicon group represented by general formula (1): -Si(R 1 ) 3-a (X) a (1)
• R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; The substituent may have a heteroatom.
• Each X is independently a hydroxyl group or a hydrolyzable group; a is 1, 2 or 3.
• the curable composition according to one embodiment of the present invention contains a crystalline polyoxyalkylene polymer (A) and a silanol condensation catalyst (B).
• a polyoxyalkylene polymer capable of producing a cured product having excellent elastic modulus and strength, and a curable composition containing the same.
• Crystalline polyoxyalkylene polymer (A)] [1.1. Structure and properties of crystalline polyoxyalkylene polymer (A)]
• the crystalline polyoxyalkylene polymer (A) according to one embodiment of the present invention has a reactive silicon group represented by the general formula (1).
• the reactive silicon group is a functional group that forms a siloxane bond by a chemical reaction such as hydrolysis. -Si(R 1 ) 3-a (X) a (1)
• each R 1 independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The substituent may have a heteroatom.
• Each X independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3.
• R 1 is a hydrocarbon group having 1 to 20 carbon atoms.
• the number of carbon atoms in R 1 is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
• the hydrocarbon group may be an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent.
• the substituent may have a heteroatom.
• a heteroatom refers to an atom of a type other than carbon and hydrogen atoms. Suitable examples of heteroatoms include N, O, S, P, Si, and halogen atoms (F, Cl, Br, I, etc.).
• a substituent having a heteroatom is referred to as a heteroatom-containing substituent.
• 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.
• heteroatom-containing substituents include hydroxyl groups; mercapto groups; halogen atoms (Cl, Br, I, F, etc.); nitro groups; cyano groups; alkoxy groups (methoxy groups, ethoxy groups, n-propyloxy groups, isopropyloxy groups, etc.); alkylthio groups (methylthio groups, ethylthio groups, n-propylthio groups, isopropylthio groups, etc.); acyl groups (acetyl groups, propionyl groups, butanoyl groups, etc.); acyloxy groups (acetyloxy groups, propionyloxy groups, butanoyloxy groups, etc.); substituted or unsubstituted amino groups (amino groups, methylamino groups, ethylamino groups, dimethylamino groups, diethylamino groups, etc.); substituted or unsubstituted aminocarbonyl groups (amino groups
• R 1 has a heteroatom-containing substituent
• the total number of carbon atoms and heteroatoms in R 1 as a whole is preferably 2 to 30, more preferably 2 to 18, even more preferably 2 to 10, and particularly preferably 2 to 6.
• R 1 examples include alkyl groups (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 groups); alkenyl groups (vinyl, cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohex
• R 1 Groups in which one or more hydrogen atoms contained in these hydrocarbon groups have been substituted with the above-mentioned heteroatom-containing substituents are also preferred as R 1 .
• R 1 examples include alkyl groups (such as methyl and ethyl groups); alkyl groups having heteroatom-containing substituents (such as chloromethyl and methoxymethyl groups); cycloalkyl groups (such as cyclohexyl groups); aryl groups (such as phenyl groups); and aralkyl groups (such as benzyl groups).
• R 1 is independently selected from the group consisting of methyl groups, methoxymethyl groups, and chloromethyl groups. More preferably, R 1 is independently selected from the group consisting of methyl groups and methoxymethyl groups. Even more preferably, R 1 is a methyl group.
• a is 1, 2 or 3.
• a is 2 or 3. It is more preferable that a is 3, since this improves the curability of the curable composition and the strength of the cured product.
• X is a hydroxyl group or a hydrolyzable group.
• hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups.
• alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle.
• the alkoxy groups are preferably independently selected from methoxy groups and ethoxy groups, and more preferably methoxy groups.
• reactive silicon groups represented by formula (1) include 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.
• trimethoxysilyl, (chloromethyl)dimethoxysilyl, and (methoxymethyl)dimethoxysilyl are preferred, with trimethoxysilyl being more preferred.
• the main chain of the crystalline polyoxyalkylene polymer (A) has a repeating unit represented by -R 3 -O-, where R 3 is a divalent branched alkylene group having 1 to 14 carbon atoms.
• R 3 is a divalent branched alkylene group having 1 to 14 carbon atoms.
• the polyoxyalkylene polymer (A) is a polyoxypropylene polymer.
• the proportion of repeating units represented by -R 3 -O- is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more.
• the main chain of the crystalline polyoxyalkylene polymer (A) may have two or more kinds of repeating units represented by -R 3 -O-.
• the proportion of repeating units represented by -CH 2 CH(CH 3 )O- may be 50% or more, 70% or more, or 90% or more.
• the crystallinity of a polyoxyalkylene polymer is determined by the isotacticity of the main chain. Specifically, a polyoxyalkylene polymer with a high content of mm-triads can be said to be crystalline (in this specification, the "m” in "mm-triad” stands for “meso”).
• the mm-triad content can be calculated by the method described in J. AM. CHEM. SOC., vol. 127, pp. 11566-11567 (2005).
• the mm-triad content of the crystalline polyoxyalkylene polymer (A) is preferably 5% or more, more preferably 25% or more, even more preferably 50% or more, and particularly preferably 75% or more, from the viewpoint of the elastic modulus and strength of the cured product.
• the isotactic structures of the crystalline polyoxyalkylene polymer (A) may be distributed in any part of the main chain.
• the isotactic structures and atactic structures may be randomly distributed in the main chain.
• the isotactic structures and atactic structures may form blocks (isotactic structure-atactic structure-isotactic structure, atactic structure-isotactic structure-atactic structure, etc.). By forming blocks in this way, the resulting cured product may exhibit better mechanical properties.
• the main chain of the crystalline polyoxyalkylene polymer (A) may be linear or branched.
• the number average molecular weight of the crystalline polyoxyalkylene polymer (A) is not particularly limited.
• the lower limit of the number average molecular weight is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more.
• the upper limit of the number average molecular weight is preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less.
• the number average molecular weight of the crystalline polyoxyalkylene polymer (A) is determined as a polystyrene-equivalent molecular weight in GPC. If the number average molecular weight is within the above range, the polymer can be easily produced and the production cost is not excessively increased. Furthermore, if the number average molecular weight is within the above range, a cured product with high elastic modulus and strength can be obtained.
• the molecular weight distribution (Mw/Mn) of the crystalline polyoxyalkylene polymer (A) is not particularly limited, but generally, it is believed that the smaller the value, the better.
• the molecular weight distribution is preferably 3.5 or less, more preferably 3.0 or less, even more preferably 2.5 or less, and particularly preferably 2.0 or less.
• the crystalline polyoxyalkylene polymer (A) may be used alone or in combination of two or more different types.
• a reactive silicon group By utilizing the terminal hydroxyl group of the polyoxyalkylene polymer, a reactive silicon group can be introduced.
• the reactive silicon group can be introduced by the following first process. 1.
• a polyoxyalkylene polymer having a terminal hydroxyl group is allowed to react with an alkali metal salt or a composite metal cyanide complex catalyst to obtain a polyoxyalkylene polymer having a terminal metaloxy group.
• An electrophilic agent having a carbon-carbon unsaturated bond is allowed to act on a polyoxyalkylene polymer having a metaloxy group at its terminal, thereby obtaining a polyoxyalkylene polymer having a carbon-carbon unsaturated bond at its terminal portion.
• a polyoxyalkylene polymer having a terminal carbon-carbon unsaturated bond is reacted with a reactive silicon group-containing compound that reacts with the carbon-carbon unsaturated bond to obtain a polyoxyalkylene polymer having a terminal reactive silicon group.
• the alkali metal salt in step 1 is not particularly limited.
• alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide.
• sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred from the viewpoints of ease of handling and solubility, and sodium methoxide and sodium tert-butoxide are more preferred.
• sodium methoxide is preferred from the viewpoint of availability.
• An alkali metal salt dissolved in a solvent may be used in the reaction.
• the electrophile having a carbon-carbon unsaturated bond in step 2 is not particularly limited.
• Examples of electrophiles having a carbon-carbon unsaturated bond include organic halides having a carbon-carbon unsaturated bond and epoxy compounds having a carbon-carbon unsaturated bond.
• An organic halide having a carbon-carbon unsaturated bond and a metaloxy group form an ether bond through a halogen substitution reaction. This introduces a carbon-carbon unsaturated bond into the terminal portion of the polyoxyalkylene polymer.
• organic halides having carbon-carbon unsaturated bonds include 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 because they are easy to handle.
• methallyl chloride, methallyl bromide, and methallyl iodide are preferred because they improve the average number of reactive silicon groups introduced relative to the number of ends of the main chain of the polyoxyalkylene polymer.
• the organic halide having a carbon-carbon unsaturated bond may be a halogenated hydrocarbon compound having a carbon-carbon triple bond.
• a polyoxyalkylene polymer having a carbon-carbon triple bond at the terminal portion is obtained.
• a reactive silicon group is introduced into a polyoxyalkylene polymer having a carbon-carbon triple bond at the terminal portion, a polyoxyalkylene polymer having a carbon-carbon double bond adjacent to the reactive silicon group is obtained.
• 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-butyne, 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-octyn
• a halogenated hydrocarbon compound having a carbon-carbon triple bond and a halogenated hydrocarbon compound having a carbon-carbon double bond may be used in combination.
• An epoxy compound having a carbon-carbon unsaturated bond and a metaloxy group form an ether bond through a ring-opening addition reaction of the epoxy group. This results in a polyoxyalkylene polymer having both a carbon-carbon unsaturated bond and a metaloxy group at the end portion.
• the ring-opening addition reaction by adjusting the amount of epoxy compound used relative to the metaloxy group or the reaction conditions, it is possible to add an epoxy compound having one or more carbon-carbon unsaturated bonds to one metaloxy group.
• the epoxy compound having a carbon-carbon unsaturated bond is not particularly limited. From the viewpoint of reactivity, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monoxide are preferred, and allyl glycidyl ether is more preferred.
• step 3 it is preferable to carry out a hydrosilylation reaction between a polyoxyalkylene polymer having a carbon-carbon unsaturated bond at the terminal portion and a hydrosilane compound having a reactive silicon group.
• the advantages of using a hydrosilylation reaction include that it can be carried out easily, the amount of reactive silicon group introduced can be easily adjusted, and the physical properties of the resulting polymer are stable.
• hydrosilane compounds having reactive silicon groups include halosilanes, alkoxysilanes, acyloxysilanes, ketoximate silanes, and isopropenyloxysilane (deacetone type).
• halosilanes include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane.
• alkoxysilanes include trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane,
• the acyloxysilane include diacetoxymethylsilane and diacetoxyphenylsilane.
• Examples of the ketoximate silane include bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane.
• Examples of the acyloxysilane include diacetoxymethylsilane and diacetoxyphenylsilane.
• Examples of the ketoximate silane include bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane.
• Examples of isopropenyloxysilanes (deacetone type) include triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.
• the hydrosilylation reaction in step 3 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.
• More specific examples include platinum supported on a carrier such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid and an alcohol, aldehyde, or ketone; platinum-olefin complexes (Pt(CH 2 ⁇ CH 2 ) 2 (PPh 3 ), Pt(CH 2 ⁇ CH 2 ) 2 Cl 2, etc.); platinum-vinyl siloxane complexes (Pt ⁇ (vinyl)Me 2 SiOSiMe 2 (vinyl) ⁇ , Pt ⁇ Me(vinyl)SiO ⁇ 4 , etc.); platinum-phosphine complexes (Ph(PPh 3 ) 4 , Pt(PBu 3 ) 4 , etc.); and platinum-phosphite complexes (Pt ⁇ P(OPh) 3 ⁇ 4 , etc.). From the viewpoint of reaction efficiency, platinum catalysts are preferred, and chloroplatinic acid and platinum-vin
• the second process for introducing reactive silicon groups into the terminal hydroxyl groups of a crystalline polyoxyalkylene polymer is as follows. 1. A compound having both a reactive silicon group and an isocyanate group is allowed to act on a polyoxyalkylene polymer having a hydroxyl group at its terminal, thereby introducing a reactive silicon group via a urethane bond.
• the compound having both a reactive silicon group and an isocyanate group is not particularly limited. Specific examples of such compounds include (3-isocyanatepropyl)trimethoxysilane, (3-isocyanatepropyl)dimethoxymethylsilane, (3-isocyanatepropyl)triethoxysilane, (3-isocyanatepropyl)diethoxymethylsilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)triethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, and (isocyanatemethyl)diethoxymethylsilane.
• the urethanization reaction in step 1 may be carried out in the presence of a urethanization catalyst.
• the urethanization catalyst may be any of the conventionally known urethanization catalysts (such as those listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963). Specific examples include organotin compounds, bismuth compounds, and base catalysts (such as organic amines).
• the third process for introducing reactive silicon groups into the terminal hydroxyl groups of a crystalline polyoxyalkylene polymer is as follows. 1. An excess amount of a polyisocyanate compound is reacted with a polyoxyalkylene polymer having a hydroxyl group at the end, thereby obtaining a polymer having an isocyanate group at the end. 2. A compound having both a group that reacts with an isocyanate group (such as an amino group) and a reactive silicon group is reacted with the polymer having an isocyanate group at the end.
• polyisocyanate compounds in step 1 include aliphatic polyisocyanates (aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, etc.).
• aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate
• isophorone diisocyanate hexamethylene diisocyanate, etc.
• Examples of compounds having both a group that reacts with an isocyanate group and a reactive silicon group in step 2 include amino group-containing silanes, hydroxy group-containing silanes, and mercapto group-containing silanes.
• Examples of amino group-containing silanes include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyldimethoxymethylsilane, ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyldimethoxymethylsilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -(N-phenyl)aminopropyltrimethoxysilane, ⁇ -(N-phenyl)aminopropyldime
• Examples of hydroxyl group-containing silanes include ⁇ -hydroxypropyltrimethoxysilane and ⁇ -hydroxypropyldimethoxymethylsilane.
• Examples of mercapto group-containing silanes include ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyldimethoxymethylsilane.
• the fourth process for introducing reactive silicon groups into the terminal hydroxyl groups of a crystalline polyoxyalkylene polymer is as follows. 1. A polyoxyalkylene polymer having a terminal hydroxyl group is allowed to react with an alkali metal salt or a composite metal cyanide complex catalyst to obtain a polyoxyalkylene polymer having a terminal metaloxy group. 2. An electrophilic agent having a carbon-carbon unsaturated bond is allowed to act on a polyoxyalkylene polymer having a metaloxy group at its terminal, thereby obtaining a polyoxyalkylene polymer having a carbon-carbon unsaturated bond at its terminal portion. 3.
• a compound having both a mercaptan group and a reactive silicon group is allowed to act on a polyoxyalkylene polymer having a carbon-carbon unsaturated bond at the terminal portion, thereby introducing the reactive silicon group via a sulfide bond.
• Steps 1 and 2 are as explained in (Method 1 for introducing reactive silicon groups).
• Examples of compounds having both a mercaptan group and a reactive silicon group in step 3 include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, and (mercaptomethyl)triethoxysilane.
• step 3 the addition reaction of the mercaptan group to the carbon-carbon unsaturated bond may be carried out in the presence of a radical initiator.
• radical initiators can be used.
• Specific examples of radical initiators include azo initiators and peroxide initiators.
• catalysts with low activity against reactive silicon groups are preferred, and from this perspective, azo initiators are preferred.
• examples of azo initiators include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 2,2'-azobis(1-methylcyclohexanecarbonitrile) (V-40).
• the curable composition includes a crystalline polyoxyalkylene polymer (A) and a silanol condensation catalyst (B).
• the composition may further comprise one or more selected from the group consisting of an oxyalkylene polymer (C), a silane coupling agent (D), and a (meth)acrylic acid ester polymer having a reactive silicon group (E).
• the crystalline polyoxyalkylene polymer (A) is as explained in Section [1]. In this section, the other components will be described in detail.
• silanol condensation catalyst (B) examples include organotin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, and titanium compounds.
• 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 examples include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate.
• carboxylic acids contained in metal carboxylates include 2-ethylhexanoic acid, neodecanoic acid, oleic acid, and naphthenic acid.
• metals contained in metal carboxylates include tin, bismuth, iron, titanium, vanadium, calcium, potassium, barium, manganese, nickel, cobalt, and zirconium.
• metal carboxylates include 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 n
• zirconium oleate tetravalent
• iron oleate divalent
• iron oleate trivalent
• titanium oleate titanium oleate
• vanadium oleate trivalent
• calcium oleate divalent
• potassium oleate monovalent
• barium oleate manganese oleate
• nickel oleate nickel oleate
• cobalt oleate zirconium oleate (tetravalent)
• iron naphthenate divalent
• iron naphthenate trivalent
• titanium naphthenate titanium naphthenate
• vanadium naphthenate trivalent
• calcium naphthenate divalent
• potassium naphthenate monoovalent
• barium naphthenate manganese naphthenate
• nickel naphthenate nickel naphthenate
• iron naphthenate
• amine compounds include amines (octylamine, 2-ethylhexylamine, laurylamine, stearylamine, etc.); nitrogen-containing heterocyclic compounds (pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), etc.); guanidines (guanidine, phenylguanidine, diphenylguanidine, etc.); biguanides (butylbiguanide, 1-o-tolylbiguanide, 1-phenylbiguanide, etc.); amino group-containing silane coupling agents; and ketimine compounds.
• amines octylamine, 2-ethylhexylamine, laurylamine, stearylamine, etc.
• nitrogen-containing heterocyclic compounds pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (D
• carboxylic acids 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 examples include aluminum compounds (such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate) and zirconium compounds (such as zirconium tetrakis(acetylacetonate)).
• titanium compounds include tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis(acetylacetonate), bis(acetylacetonate)diisopropoxytitanium, and diisopropoxytitanium bis(ethylacetoacetate).
• silanol condensation catalysts (B) include fluorine anion-containing compounds, photoacid generators, photobase generators, and thermal base generators.
• the silanol condensation catalyst (B) may be used alone or in combination of two or more different types.
• the lower limit of the content of the silanol condensation catalyst (B) in the curable composition is preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more, based on 100 parts by weight of the total content of the polymers having hydrolyzable silyl groups.
• the upper limit of the content of the silanol condensation catalyst (B) in the curable composition is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less, based on 100 parts by weight of the total content of the polymers having hydrolyzable silyl groups.
• the total content of the polymers having hydrolyzable silyl groups is the total content of the crystalline polyoxyalkylene polymer (A) and the amorphous polyoxyalkylene polymer (C) and (meth)acrylic acid ester polymer (E) that are optionally included.
• the content of the polymer is also included in the total content of the polymers having hydrolyzable silyl groups.
• Amorphous polyoxyalkylene polymer (C) The mm-triad content of the amorphous polyoxyalkylene polymer (C) is preferably less than 5%.
• the amorphous polyoxyalkylene polymer (C) has a reactive silicon group represented by the general formula (2). -Si(R 2 ) 3-b (Y) b (2)
• R2 's each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The substituent may have a heteroatom.
• Y's each independently represent a hydroxyl group or a hydrolyzable group.
• b is 1, 2, or 3.
• R2 is the same as that of R1 in Section [1].
• Y is the same as that of X in Section [1].
• Y is preferably an alkoxy group, more preferably a methoxy group.
• b is 1, 2 or 3.
• b is 2 or 3. Since the curable composition has good curability and the cured product has good strength, b is more preferably 3.
• Examples of reactive silicon groups represented by formula (2) include those exemplified for the crystalline polyoxyalkylene polymer (A). Specific examples include 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.
• the dimethoxymethylsilyl, trimethoxysilyl, triethoxysilyl, and (methoxymethyl)dimethoxysilyl groups are preferred.
• a trimethoxysilyl group, a (chloromethyl)dimethoxysilyl group, or a (methoxymethyl)dimethoxysilyl group is preferred, with a trimethoxysilyl group being more preferred.
• the main chain of the amorphous polyoxyalkylene polymer (C) has a repeating unit represented by -R 4 -O-.
• R 4 is a divalent functional group having 1 to 14 carbon atoms, preferably a divalent functional group having 2 to 4 carbon atoms.
• R 4 is preferably an alkylene group.
• the alkylene group may be linear or branched.
• Specific examples of the repeating unit represented by -R 4 -O- include -CH 2 O-, -CH 2 CH 2 O-, -CH 2 CH(CH 3 )O-, -CH 2 C(CH 3 )(CH 3 )O-, and -CH 2 CH 2 CH 2 CH 2 O-.
• the polyoxyalkylene polymer (C) is a polyoxypropylene polymer.
• the proportion of repeating units represented by -R 3 -O- is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more.
• the main chain of the amorphous polyoxyalkylene polymer (C) may have two or more kinds of repeating units represented by -R 3 -O-.
• the proportion of repeating units represented by -CH 2 CH(CH 3 )O- may be 50% or more, 70% or more, or 90% or more.
• the main chain of the amorphous polyoxyalkylene polymer (C) may be linear or branched.
• the number average molecular weight of the amorphous polyoxyalkylene polymer (C) is not particularly limited.
• the lower limit of the number average molecular weight is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 12,000 or more, and particularly preferably 13,000 or more.
• the upper limit of the number average molecular weight is preferably 100,000 or less, more preferably 40,000 or less, even more preferably 25,000 or less, and particularly preferably 20,000 or less.
• the number average molecular weight of the amorphous polyoxyalkylene polymer (C) is determined as a polystyrene-equivalent molecular weight in GPC.
• the polymer When the number average molecular weight is within the above-mentioned range, the polymer can be easily produced and the production cost is not excessively increased. Furthermore, when the number average molecular weight is within the above-mentioned range, a cured product with high strength can be obtained.
• the molecular weight distribution (Mw/Mn) of the amorphous polyoxyalkylene polymer (C) is not particularly limited, but is preferably narrow.
• the molecular weight distribution is preferably 1.6 or less, more preferably 1.4 or less, even more preferably 1.3 or less, and particularly preferably 1.2 or less.
• the number average molecular weight and weight average molecular weight of the amorphous polyoxyalkylene polymer (C) are determined as polystyrene-equivalent molecular weights in GPC.
• the main chain of the amorphous polyoxyalkylene polymer (C) can be formed by a conventional method. For example, it can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group. This results in a polyoxyalkylene polymer having a hydroxyl group at its terminal. Since the molecular weight distribution (Mw/Mn) of the resulting polymer is narrow, a polymerization method using a composite metal cyanide complex catalyst (such as zinc hexacyanocobaltate glyme complex) is preferred.
• a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex
• the initiator having a hydroxyl group is not particularly limited.
• examples of initiators having a hydroxyl group 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, and low molecular weight polyoxypropylene monoalkyl ether.
• an initiator having three or more hydroxyl groups may be used. Examples of such initiators include glycerin, pentaerythritol, and low molecular weight polyoxypropylene triol.
• the epoxy compound is not particularly limited.
• examples of epoxy compounds include alkylene oxides (ethylene oxide, propylene oxide, etc.) and glycidyl ethers (methyl glycidyl ether, butyl glycidyl ether, etc.).
• the epoxy compound is propylene oxide.
• the method for introducing reactive silicon groups into the amorphous polyoxyalkylene polymer (C) can be the same as that described in Section [1] in relation to the crystalline polyoxyalkylene polymer (A).
• a preferred method is to subject a polyoxyalkylene polymer having a terminal carbon-carbon unsaturated bond to a hydrosilylation reaction with a hydrosilane compound having a reactive silicon group.
• the advantages of this method include that it can be carried out easily, the amount of reactive silicon groups introduced can be easily adjusted, and the physical properties of the resulting polymer are stable.
• a commercially available product may be used as the amorphous polyoxyalkylene polymer (C).
• Specific examples of such products include SAT350, SAT400, S203H, S303H, EST280, SAX530, SAX580, SAX590, S810, S257, S258, S227, S327, MA452, and MA480 (all manufactured by Kaneka Corporation).
• a single type of amorphous polyoxyalkylene polymer (C) may be used, or two or more different types may be used in combination.
• the lower limit of the weight ratio ((A)/(C)) of the crystalline polyoxyalkylene polymer (A) to the amorphous polyoxyalkylene polymer (C) in the curable composition is preferably 1/99 or more, more preferably 10/90 or more, and even more preferably 20/80 or more.
• the upper limit of (A)/(C) is preferably 99/1 or less, more preferably 90/10 or less, and even more preferably 80/20 or less.
• silane coupling agent (D) Specific examples of the silane coupling agent (D) include amino group-containing silanes, isocyanate group-containing silanes, mercapto group-containing silanes, and epoxy group-containing silanes.
• amino group-containing silanes examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane.
• Examples of isocyanate group-containing silanes include ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane, ⁇ -isocyanatemethyltrimethoxysilane, and ⁇ -isocyanatemethyldimethoxymethylsilane.
• Examples of mercapto group-containing silanes include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, and ⁇ -mercaptopropylmethyldimethoxysilane.
• Examples of epoxy group-containing silanes include ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
• silane coupling agent (D) a condensate or reaction product of the silane coupling agent (D) may be used.
• condensates of the silane coupling agent (D) include condensates of aminosilanes and condensates of aminosilanes and other alkoxysilanes.
• reaction products of the silane coupling agent include reaction products of aminosilanes and epoxysilanes and reaction products of aminosilanes and (meth)acrylic group-containing silanes.
• Specific examples of such silane coupling agents (D) include Dynasylan 1146 and Dynasylan 1124 (EVONIK).
• the silane coupling agent (D) may be used alone or in combination of two or more different types.
• the lower limit of the content of the silane coupling agent (D) in the curable composition is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, based on 100 parts by weight of the total content of the polymers having a hydrolyzable silyl group.
• the upper limit of the content of the silane coupling agent (D) in the curable composition is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total content of the polymers having a hydrolyzable silyl group.
• the total content of the polymers having a hydrolyzable silyl group is the total content of the crystalline polyoxyalkylene polymer (A) and the amorphous polyoxyalkylene polymer (C) and (meth)acrylic acid ester polymer (E) that are optionally included.
• the content of the polymer is also included in the total content of the polymers having a hydrolyzable silyl group.
• the curable composition may further contain a (meth)acrylic acid ester-based polymer (E) having a reactive silicon group.
• (meth)acrylic means acrylic and/or methacrylic.
• the (meth)acrylic acid ester monomer constituting the main chain of the (meth)acrylic acid ester polymer (E) is not particularly limited. Specific examples of the monomer 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, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl
• the main chain of the (meth)acrylic acid ester polymer (E) may have a repeating unit derived from a (meth)acrylic monomer other than a (meth)acrylic acid ester monomer.
• (meth)acrylic monomers include acrylic acid monomers (acrylic acid, methacrylic acid, etc.); monomers having an amide group (N-methylol acrylamide, N-methylol methacrylamide, etc.), monomers having an epoxy group (glycidyl acrylate, glycidyl methacrylate, etc.), and monomers having a nitrogen-containing group (diethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc.).
• the main chain of the (meth)acrylic acid ester polymer (E) may have a repeating unit derived from a vinyl monomer.
• the vinyl monomer is not particularly limited. Examples of the vinyl monomer include styrene monomers (styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, styrenesulfonic acid and its salts, etc.); vinyl monomers containing fluorine (perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc.); vinyl monomers containing silicon (vinyltrimethoxysilane, vinyltriethoxysilane, etc.); maleic acid monomers (maleic anhydride, maleic acid, monoalkyl esters of maleic acid, dialkyl esters of maleic acid, etc.); fumaric acid monomers (fumaric acid, monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid, etc.); maleimi
• vinyl monomer examples include ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc.); vinyl monomers having a nitrile group (acrylonitrile, methacrylonitrile, etc.); vinyl monomers having an amide group (acrylamide, methacrylamide, etc.); vinyl ester monomers (vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc.); alkenyl monomers (ethylene, propylene, etc.); conjugated diene monomers (butadiene, isoprene, etc.); vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These vinyl monomers may be used alone or in combination of two or more different types.
• the repeating units constituting the main chain of the (meth)acrylic acid ester polymer (E) are preferably one or more types selected from the group consisting of styrene-based monomers and (meth)acrylic acid-based monomers, more preferably one or more types selected from the group consisting of acrylic acid ester monomers and methacrylic acid ester monomers, and even more preferably one or more types selected from the group consisting of acrylic acid ester monomers.
• the proportion of repeating units derived from (meth)acrylic acid ester monomers among all repeating units constituting the main chain of the (meth)acrylic acid ester polymer (E) is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more.
• the lower limit of the number of reactive silicon groups contained in the (meth)acrylic acid ester polymer (E) is preferably 1.0 or more on average per molecule, and from the viewpoint of the mechanical properties of the cured product, 1.27 or more is more preferable.
• the upper limit of the number of reactive silicon groups is preferably 5.0 or less, and from the viewpoint of the stability of the polymer, 3.0 or less is more preferable.
• the (meth)acrylic acid ester polymer (E) has a reactive silicon group represented by the general formula (3). -SiR 5 3-c Z c (3)
• each R5 independently represents a hydrocarbon group having 1 to 20 carbon atoms.
• the substituent may have a heteroatom.
• Each Z independently represents a hydroxyl group or a hydrolyzable group. c is 1, 2, or 3. It is expressed as:
• R5 is a hydrocarbon group having 1 to 20 carbon atoms.
• the number of carbon atoms in R5 is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4.
• the hydrocarbon group may be an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent.
• R5 include alkyl groups (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 groups); alkenyl groups (vinyl, cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexy
• R5 examples include alkyl groups (methyl, ethyl, etc.); alkyl groups having a heteroatom-containing substituent (chloromethyl, methoxymethyl, etc.); cycloalkyl groups (cyclohexyl, etc.); aryl groups (phenyl, etc.); and aralkyl groups (benzyl, etc.).
• R5 is independently selected from the group consisting of a methyl group, a methoxymethyl group, and a chloromethyl group. More preferably, R5 is independently selected from the group consisting of a methyl group and a methoxymethyl group. Even more preferably, R5 is a methyl group.
• Z is a hydroxyl group or a hydrolyzable group.
• hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups.
• alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle.
• the alkoxy groups are preferably independently selected from methoxy groups and ethoxy groups, and more preferably methoxy groups.
• c is 1, 2 or 3.
• c is 2 or 3.
• reactive silicon groups represented by formula (3) include 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.
• the dimethoxymethylsilyl, trimethoxysilyl, triethoxysilyl, and (methoxymethyl)dimethoxysilyl groups are preferred.
• the trimethoxysilyl and (methoxymethyl)dimethoxysilyl groups are preferred, and the trimethoxysilyl group is more preferred.
• the number average molecular weight of the (meth)acrylic acid ester polymer (E) is not particularly limited.
• the lower limit of the number average molecular weight is preferably 500 or more, and more preferably 1,000 or more.
• the upper limit of the number average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.
• the number average molecular weight of the (meth)acrylic acid ester polymer (E) is determined as a polystyrene-equivalent molecular weight in GPC.
• the molecular weight distribution (Mw/Mn) of the (meth)acrylic acid ester polymer (E) is not particularly limited, but is preferably narrow.
• the molecular weight distribution is preferably 2.5 or less, more preferably 2.0 or less, even more preferably 1.5 or less, and particularly preferably 1.2 or less.
• the number average molecular weight and weight average molecular weight of the (meth)acrylic acid ester polymer (E) are determined as polystyrene-equivalent molecular weights in GPC.
• the (meth)acrylic acid ester polymer (E) may be used alone or in combination of two or more different types.
• Method 1 A method of copolymerizing a compound having both a polymerizable unsaturated group and a reactive silicon group with the above-mentioned monomer.
• the (meth)acrylic acid ester polymer (E) obtained by this method has reactive silicon groups randomly introduced into the main chain.
• Method 2 A method of polymerizing a (meth)acrylic acid ester polymer using a mercaptosilane compound having a reactive silicon group as a chain transfer agent.
• the (meth)acrylic acid ester polymer (E) obtained by this method has a reactive silicon group introduced at the end of the main chain.
• Method 3 A compound having both a polymerizable unsaturated group and a reactive functional group is copolymerized with the above-mentioned monomer. Then, a compound having both a functional group that reacts with the reactive functional group and a reactive silicon group is reacted.
• a specific example of this method is a method in which the above-mentioned monomer is copolymerized with 2-hydroxyethyl acrylate, and then the hydroxyl group contained in the main chain is reacted with an isocyanate silane having a reactive silicon group.
• Another specific example is a method in which the above-mentioned monomer is copolymerized with glycidyl acrylate, and then the epoxy group contained in the main chain is reacted with an aminosilane compound having a reactive silicon group.
• Method 4 A method of modifying the terminal functional groups of a (meth)acrylic acid ester polymer synthesized by living radical polymerization to introduce reactive silicon groups.
• a (meth)acrylic acid ester polymer obtained by living radical polymerization is easy to introduce functional groups to the polymer terminals.
• reactive silicon groups can be introduced to the terminals of the main chain. This method produces a polymer with a narrow molecular weight distribution.
• the molecular weight distribution is preferably 1.6 or less, more preferably 1.4 or less, and even more preferably 1.2 or less.
• the number average molecular weight and weight average molecular weight of the (meth)acrylic acid ester polymer (E) are determined as polystyrene-equivalent molecular weights in GPC.
• examples of compounds having both a polymerizable unsaturated group and a reactive silicon group include 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(dimethoxymethylsilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, (trimethoxysilyl)methyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, (triethoxysilyl)methyl (meth)acrylate, (diethoxymethylsilyl)methyl (meth)acrylate, and 3-((methoxymethyl)dimethoxysilyl)propyl (meth)acrylate. From the viewpoint of availability, trimethoxysilylpropyl (meth)acrylate and (dimethoxymethylsilyl)propyl (meth)acrylate are preferred among the above.
• examples of mercaptosilane compounds having a reactive silicon group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, and mercaptomethyltriethoxysilane.
• examples of compounds having both a polymerizable unsaturated group and a reactive functional group include isocyanate silane compounds (3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl dimethoxy methyl silane, 3-isocyanate propyl triethoxy silane, isocyanate methyl trimethoxy silane, isocyanate methyl triethoxy silane, isocyanate methyl dimethoxy methyl silane, isocyanate methyl diethoxy methyl silane, etc.); epoxy silane compounds (3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-glycidoxypropyl dimethoxy methyl silane, glycidoxy methyl trimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane, glycidoxymethyldiethoxymethylsilane, etc.); aminosilane
• Modification reactions that can be used in Method 4 include the following.
• a (meth)acrylic acid ester-based polymer having a terminal reactive group is obtained by polymerization, and then reacted with a compound having both a reactive silicon group and a functional group capable of reacting with the terminal reactive group.
• a (meth)acrylic acid ester polymer having a terminal reactive group is obtained by polymerization.
• a compound having both a functional group and a double bond that can react with the terminal reactive group is reacted. This introduces a double bond to the polymer terminal.
• a reactive silicon group is introduced by a hydrosilylation reaction or the like.
• Methods 1 to 4 may be combined in any manner. For example, combining methods 2 and 3 will produce a (meth)acrylic acid ester polymer (E) that has reactive silicon groups both in the main chain and at the ends.
• E (meth)acrylic acid ester polymer
• the curable composition may contain components other than those described above. Examples of such components include fillers, adhesion promoters, plasticizers, solvents, diluents, sagging inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, physical property adjusters, tackifier resins, compounds having epoxy groups, photocurable substances, oxygen curable substances, epoxy resins, and other resins. Furthermore, the curable composition may contain additives for adjusting the physical properties of the curable composition or the cured product.
• additives examples include surface improvers, foaming agents, curability adjusters, flame retardants, silicates, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.
• the total content of the curable polymer means the total content of substances that are crosslinked and contribute to the formation of a cured product.
• the curable polymer includes polymers having hydrolyzable silyl groups and other curable polymers (such as epoxy resins).
• the total content of the curable polymer is the total content of the crystalline polyoxyalkylene polymer (A) and the optionally contained amorphous polyoxyalkylene polymer (C), (meth)acrylic acid ester polymer (E), and epoxy resin.
• Fillers examples include ground 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 fibers and filaments.
• the content of the filler in the curable composition is preferably 1 to 600 parts by weight, and more preferably 10 to 300 parts by weight, based on 100 parts by weight of the total content of the curable polymer. Only one type of filler may be used, or two or more different types may be used in combination.
• Balloons are spherical fillers with a hollow interior.
• Balloon materials include inorganic materials (glass, shirasu, silica, etc.) and organic materials (phenolic resin, urea resin, polystyrene, saran, etc.).
• the balloon content in the curable composition is preferably 0.1 to 100 parts by weight, and more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total content of the curable polymer. Only one type of balloon may be used, or two or more different types may be used in combination.
• plasticizer examples include phthalate compounds (dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, etc.); terephthalate compounds (bis(2-ethylhexyl)-1,4-benzenedicarboxylate, etc.); and non-phthalate compounds (1,2-cyclohexanedicarboxylic acid diisononyl ester, etc.
• phthalate compounds dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, etc.
• terephthalate compounds bis(2-ethylhexyl)-1
• Specific examples of products include Hexamol DINCH (BASF), etc.); aliphatic polycarboxylic acid ester compounds (dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, acetyl tributyl citrate, etc.); unsaturated fatty acid ester compounds (butyl oleate, methyl acetylricinoleate, etc.); alkylsulfonic acid phenyl esters (specific product examples include Mesamoll (LANXESS), etc.); phosphate ester compounds; trimellitic acid ester compounds; hydrocarbon-based oils (chlorinated paraffins, alkyl diphenyls, partially hydrogenated terphenyls, etc.); process oils; and epoxy plasticizers (epoxidized soybean oil, epoxy benzyl stearate, etc.).
• aliphatic polycarboxylic acid ester compounds dioctyl
• the plasticizer may be a polymer plasticizer.
• polymer plasticizers include vinyl polymers, polyester plasticizers, polyether polyols (polyethylene glycol, polypropylene glycol, etc., having a number average molecular weight of 500 or more), derivatives in which the hydroxyl groups of polyether polyols are converted to ester groups, ether groups, etc., polystyrenes, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene.
• the content of the plasticizer in the curable composition is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, based on 100 parts by weight of the total content of the curable polymer. If the content is 5 parts by weight or more, the effect as a plasticizer can be expected to be sufficient. If the content is 150 parts by weight or less, sufficient mechanical strength can be imparted to the cured product. Only one type of plasticizer may be used, or two or more different types may be used in combination.
• solvent and diluents examples include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers.
• 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. Only one type of solvent and/or diluent may be used, or two or more different types may be used in combination.
• Anti-sagging agent By blending an anti-sagging agent in the curable composition, sagging of the curable composition is prevented and workability is improved.
• the anti-sagging agent include polyamide waxes, hydrogenated castor oil derivatives, and metal soaps (calcium stearate, aluminum stearate, barium stearate, etc.).
• the content of the anti-sagging agent in the curable composition is preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total content of the curable polymer. Only one type of anti-sagging agent may be used, or two or more different types may be used in combination.
• antioxidants By blending an antioxidant in the curable composition, the weather resistance of the cured product is improved.
• examples of the antioxidant include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based. Specific examples of products include BHT, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520, and SONGNOX 1076.
• a hindered amine-based light stabilizer may be blended as an antioxidant.
• Specific examples of products include Tinuvin 622LD, Tinuvin 144, Tinuvin 292, CHIMASSORB 944LD, and CHIMASSORB 119FL (all from BASF); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, and ADK STAB LA-68 (all from ADEKA Corporation); SANOL LS-2626, SANOL LS-1114, and SANOL LS-744 (all from Sankyo Lifetech Co., Ltd.); and NOCRAC CD (Ouchi Shinko Chemical Industry Co., Ltd.).
• Further examples of antioxidant products include SONGNOX 4120, Nauguard 445, and OKABEST CLX050.
• antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
• the content of the antioxidant in the curable composition is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total content of the curable polymer. Only one type of antioxidant may be used, or two or more different types may be used in combination.
• Light stabilizer By blending a light stabilizer in the curable composition, photo-oxidative deterioration of the cured product can be prevented.
• light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based. Among the above, hindered amine-based stabilizers are 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, Tinuvin B97, CHIMASSORB 119 FL, and CHIMASSORB 944 LD (all from BASF); ADK STAB LA-57, LA-62, LA-63, LA-67, and LA-68 (all from ADEKA CORPORATION); SANOL LS-292, LS-2626, LS-765, LS-744, and LS-1114 (all from Sankyo Lifetech Co., Ltd.); SABOSTAB UV91, SABOSTAB UV119, SONGSORB CS5100, and SONGSORB Examples include CS622, SONGSORB CS944 (both SONGWON), and Nocrac CD (Ouchi Shinko Chemical Industry Co., Ltd.).
• the content of the light stabilizer in the curable composition is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total content of the curable polymer. Only one type of light stabilizer may be used, or two or more different types may be used in combination.
• ultraviolet absorber By blending an ultraviolet absorber in the curable composition, the surface weather resistance of the cured product is improved.
• ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, triazine-based, substituted acrylonitrile-based, and metal chelate-based. Among these, benzotriazole-based is preferred.
• benzotriazole-based ultraviolet absorbers include Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 1600 (all BASF); SONGSORB 3290 (SONGWON).
• triazine-based UV absorbers include Tinuvin 400, Tinuvin 405, Tinuvin 477, Tinuvin 1577ED (all BASF); SONGSORB CS400, SONGSORB 1577 (SONGWON).
• benzophenone-based UV absorbers include SONGSORB 8100 (SONGWON).
• An example of such a product is Addworks IBC760 (Clariant).
• the content of the ultraviolet absorber in the curable composition is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total content of the curable polymer. Only one type of ultraviolet absorber may be used, or two or more different types may be used in combination.
• property adjusters include alkylalkoxysilanes (phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, etc.); arylalkoxysilanes (diphenyldimethoxysilane, phenyltrimethoxysilane, etc.); alkylisopropenoxysilanes (dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane, etc.); trialkylsilylborates (tris(trimethylsilyl)borate, tris(triethylsilyl)borate, etc.); silicone varnish; and polysiloxanes.
• alkylalkoxysilanes phenoxytrimethylsilane, methyltrimethoxysilane, dimethyl
• compounds that generate monovalent silanol groups (preferably trimethylsilanol groups) upon hydrolysis can reduce the modulus of the cured product without increasing the stickiness of the surface of the cured product.
• examples of such compounds include alcohol derivatives of silicone compounds (examples of alcohols include hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol).
• Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.
• the content of the physical property adjuster in the curable composition is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total content of the curable polymer. Only one type of physical property adjuster may be used, or two or more different types may be used in combination.
• tackifier resin By blending a tackifier resin in the curable composition, the adhesiveness and adhesion to the substrate are improved.
• the tackifier resin include terpene resin, aromatic modified terpene resin, hydrogenated terpene resin, terpene-phenol resin, phenol resin, modified phenol resin, xylene-phenol resin, cyclopentadiene-phenol resin, coumarone-indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, styrene block copolymer and its hydrogenated product, petroleum resin (C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, and DCPD resin.
• the content of the tackifier resin in the curable composition 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, based on 100 parts by weight of the total content of the curable polymer. If the content is 2 parts by weight or more, sufficient adhesion and bonding effects to the substrate can be expected. If the content is 100 parts by weight or less, the viscosity of the curable composition does not become too high, making it easy to handle. Only one type of tackifier resin may be used, or two or more different types may be used in combination.
• Compound having an epoxy group By blending a compound having an epoxy group in the curable composition, the restorability of the cured product is improved.
• the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. More specific examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate.
• E-PS epoxy octyl stearate
• the content of the compound having an epoxy group in the curable composition is preferably 0.5 to 50 parts by weight, with the total content of the curable polymer being 100 parts by weight. Only one type of compound having an epoxy group may be used, or two or more different types may be used in combination.
• photocurable substances By blending a photocurable material in a curable composition, a film of the photocurable material is formed on the surface of the cured product, which reduces the stickiness of the surface of the cured product and improves weather resistance.
• the photocurable material is known to be an organic monomer, oligomer, resin, or a composition containing them.
• Representative examples of the photocurable material include a monomer, oligomer, or mixture thereof having one or more (meth)acrylic unsaturated groups; polyvinyl cinnamate; and azido resin.
• the content of the photocurable substance in the curable composition is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total content of the curable polymers. If the content is 0.1 part by weight or more, the effect of improving weather resistance can be expected to be sufficient. If the content is 20 parts by weight or less, the cured product does not become too hard, and cracks can be prevented. Only one type of photocurable substance may be used, or two or more different types may be used in combination.
• An oxygen-curable substance is, for example, an unsaturated compound that can react with oxygen in the air.
• a curable composition By blending an oxygen-curable substance with a curable composition, a film of a photocurable substance is formed on the surface of the cured product, which reduces stickiness of the surface of the cured product and prevents adhesion of dirt and dust.
• oxygen-curable substances examples include drying oils (tung oil, linseed oil, etc.); alkyd resins obtained by modifying drying oils; acrylic polymers, epoxy resins, or silicone resins modified with drying oils; and liquid polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene (1,2-polybutadiene, 1,4-polybutadiene, polymers of C5 to C8 dienes, etc.).
• the content of the oxygen curing substance is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total content of the curable polymer. If the content is 0.1 part by weight or more, a sufficient effect of improving contamination can be expected. If the content is 20 parts by weight or less, the mechanical strength of the cured product is less likely to be impaired. Only one type of oxygen curing substance may be used, or two or more different types may be used in combination. In addition, an oxygen curing substance and a photocuring substance may be used in combination (see JP-A-3-160053, etc.).
• epoxy resin The curable composition containing the epoxy resin is particularly preferable as an adhesive (particularly an adhesive for exterior wall tiles).
• the epoxy resin include bisphenol A type epoxy resins and novolac type epoxy resins.
• the content of the epoxy resin, crystalline polyoxyalkylene polymer (A) and amorphous polyoxyalkylene polymer (C) is preferably in the range of (100/1) to (1/100) in terms of weight ratio, i.e., total content of crystalline polyoxyalkylene polymer (A) and amorphous polyoxyalkylene polymer (C) / content of epoxy resin. If the amount of epoxy resin is too small, it is difficult to obtain the improved impact strength and toughness resulting from the epoxy resin cured product. If the amount of epoxy resin is too large, the strength of the cured product tends to be insufficient.
• the curable composition may further contain an epoxy resin curing agent for curing the epoxy resin.
• an epoxy resin curing agent for curing the epoxy resin.
• the epoxy resin curing agent any commonly used epoxy resin curing agent can be used.
• the content of the epoxy resin curing agent in the curable composition is preferably 0.1 to 300 parts by weight, assuming that the epoxy resin content is 100 parts by weight.
• the curable composition may be a one-component curable composition or a two-component curable composition.
• a one-component curable composition all components are mixed as one composition.
• the one-component curable composition is sealed and stored before use, and is cured by moisture in the air after use.
• a two-component curable composition the components are mixed separately into two compositions, a base agent and a curing agent.
• the curing agent includes components such as a curing catalyst, a filler, a plasticizer, and water.
• the base agent and the curing agent are mixed before use. From the viewpoint of workability, a one-component curable composition is preferred.
• alkoxysilane compounds include n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane.
• the content of the dehydrating agent (especially a silicon compound that can react with water, such as vinyltrimethoxysilane) is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total content of the curable polymer.
• the curable composition can be used as an 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 one embodiment of the present invention has excellent flexibility and adhesiveness. Therefore, it is more preferable to use it as a sealing material or an adhesive among the above-mentioned.
• curable compositions include electrical and electronic component materials (such as solar cell backside sealing materials), electrical and electronic components (such as insulating coating materials for electric wires and cables), electrical insulation materials for equipment, acoustic insulation materials, elastic adhesives, binders, contact adhesives, spray-type sealants, crack repair materials, tiling adhesives, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealants, dental impression materials, food packaging materials, exterior materials (sizing boards, etc.) Sealing materials for joints of glass, 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 devices, films, gaskets, concrete reinforcing materials, temporary adhesives, molding materials, rust-proofing and waterproofing sealants for wired glass and laminated glass ends (cut parts), liquid sealants used in automobile parts, large vehicle parts (trucks, buses, etc.), train car
• the curable composition adheres to various substrates such as glass, porcelain, wood, metal, and resin moldings. Therefore, it can also be used in various types of sealing compositions or adhesive compositions.
• the curable composition can also be used as an adhesive material such as adhesive tape or sheet.
• R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; The substituent may have a heteroatom.
• Each X is independently a hydroxyl group or a hydrolyzable group; a is 1, 2 or 3.
• ⁇ 3> The crystalline polyoxyalkylene polymer (A) according to ⁇ 2>, wherein X is a methoxy group.
• ⁇ 4> The crystalline polyoxyalkylene polymer (A) according to any one of ⁇ 1> to ⁇ 3>, wherein the crystalline polyoxyalkylene polymer (A) is a polyoxypropylene polymer.
• ⁇ 5> A crystalline polyoxyalkylene polymer (A) according to any one of ⁇ 1> to ⁇ 4>, a silanol condensation catalyst (B); 1.
• a curable composition comprising: ⁇ 6> The curable composition according to ⁇ 5>, further comprising an amorphous polyoxyalkylene polymer (C) having a reactive silicon group represented by general formula (2): -Si(R 2 ) 3-b (Y) b (2)
• R2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; The substituent may have a heteroatom.
• Each Y is independently a hydroxyl group or a hydrolyzable group; b is 1, 2 or 3.
• ⁇ 8> The curable composition according to ⁇ 7>, wherein Y is a methoxy group.
• ⁇ 9> The curable composition according to any one of ⁇ 6> to ⁇ 8>, wherein the amorphous polyoxyalkylene polymer (C) is a polyoxypropylene polymer.
• a weight ratio ((A)/(C)) of the crystalline polyoxyalkylene polymer (A) to the amorphous polyoxyalkylene polymer (C) is 1/99 to 99/1.
• ⁇ 11> The curable composition according to any one of ⁇ 5> to ⁇ 10>, further comprising a silane coupling agent (D).
• a sealant comprising the curable composition according to any one of ⁇ 5> to ⁇ 10>.
• An adhesive comprising the curable composition according to any one of ⁇ 5> to ⁇ 10>.
• ⁇ 14> A cured product obtained by curing the curable composition according to any one of ⁇ 5> to ⁇ 10>.
• the reaction solution was neutralized with an aqueous hydrochloric acid solution and recrystallized in acetone to obtain a crystalline polyoxypropylene polymer having hydroxyl groups at the ends of the molecular chains. 4. To the resulting polymer was added 50 ppm of dibutyltin bis(isooctylmercaptopropionate) (Neostan U-360, Nitto Kasei Co., Ltd.). 5. The reaction solution was heated to 90°C, and (3-isocyanatopropyl)triethoxysilane (Tokyo Chemical Industry Co., Ltd.) was added dropwise. The reaction was allowed to proceed in this state for 5 hours.
• the peak top molecular weight in step 1 is a polystyrene equivalent molecular weight measured by GPC. Specific measurement conditions are as follows. ⁇ Liquid delivery system: HLC-8120GPC (Tosoh Corporation) Column: TSK-GEL H type (Tosoh Corporation) Solvent: Chloroform
• the mm-triad content of the obtained polyoxypropylene-based polymer was 99% or more. This proves that a crystalline polyoxypropylene-based resin was obtained.
• the mm-triad content was confirmed by 13 C NMR in the same manner as described in J. AM. CHEM. SOC., vol. 127, pp. 11566-11567 (2005).
• the amount of NaOMe added was 1.2 molar equivalents relative to the amount of hydroxyl groups in the polymer. 3. Allyl chloride was added to convert the terminal hydroxyl groups to allyl groups, and then the unreacted allyl chloride was removed by volatilization under reduced pressure. 4. 100 parts by weight of the crude polymer, 300 parts by weight of n-hexane, and 300 parts by weight of water were mixed and stirred, and then the water was removed by centrifugation. 5. 300 parts by weight of water was mixed and stirred into the hexane solution of the obtained polymer. Then, the water was removed by centrifugation. Then, the hexane was removed by devolatilization under reduced pressure.
• a polypropylene oxide polymer having an allyl group at the end of the molecule was obtained.
• the number average molecular weight of this polymer was about 14,500. 6.
• the obtained polymer was reacted with methyldimethoxysilane at 90°C for 5 hours.
• a polyoxypropylene polymer having methyldimethoxysilyl groups at the ends of the molecular chains was obtained.
• the amount of methyldimethoxysilane added was 0.8 molar equivalents relative to the allyl groups contained in the polymer.
• As a catalyst a 2-propanol solution of platinum vinylsiloxane complex (platinum content: 3 wt%) was used.
• the amount of catalyst added was 150 ppm, based on 100 parts by weight of the polymer to be reacted.
• the number of methyldimethoxysilyl groups calculated from the 1H NMR spectrum was about 1.6 per molecule.
• the number average molecular weight in step 1 is a polystyrene equivalent molecular weight measured by GPC. Specific measurement conditions are as follows. ⁇ Liquid delivery system: HLC-8120GPC (Tosoh Corporation) Column: TSK-GEL H type (Tosoh Corporation) Solvent: Tetrahydrofuran
• the mm-triad content of the resulting polyoxypropylene polymer was less than 5%. This proves that an amorphous polyoxypropylene resin was indeed obtained.
• Example 1 A cured product was prepared according to the following procedure. 1. A crystalline polyoxypropylene-based polymer and an amorphous polyoxypropylene-based polymer were added to a mayonnaise bottle. Both of these polyoxypropylene-based polymers had reactive silicon groups introduced therein. 2. 100 parts by weight of tetrahydrofuran was added to the total content of the polyoxypropylene polymers of 100 parts by weight, and the mixture was then mixed while being heated in an oven at 70°C. 3. The mixture was removed from the oven and a silanol condensation catalyst and water were added. After stirring with a spatula, the curable composition was poured into a mold.
• Dibutyltin dilaurate (Neostan U-100, Nitto Kasei Co., Ltd.) was used as the silanol condensation catalyst. 4. Tetrahydrofuran was evaporated in an oven at 50° C. Then, the composition was cured at 70° C. for 20 to 33 hours. In this way, a cured product was obtained.
• Comparative Example 1 A cured product was prepared according to the following procedure. 1. A silanol condensation catalyst and water were added to an amorphous polyoxyalkylene polymer, and the mixture was stirred and poured into a mold. Dibutyltin dilaurate (Neostan U-100, Nitto Kasei Co., Ltd.) was used as the silanol condensation catalyst. 2. The product was aged for one week at a constant temperature and humidity of 23° C. and 55%. In this way, a cured product was obtained.
• Dibutyltin dilaurate Neostan U-100, Nitto Kasei Co., Ltd.
• Example 2 the crystalline polyoxypropylene-based polymer to be blended was changed to a crystalline polyoxypropylene-based polymer having no reactive silicon group. Specifically, it was changed to the crystalline polyoxypropylene-based polymer obtained in Step 2 of Synthesis Example 1. A cured product was obtained in the same manner as in Example 1 except for the above.
• the cured product of Example 1 is obtained by curing a curable composition containing a crystalline polyoxyalkylene polymer having a reactive silicon group.
• the cured product of Comparative Example 1 is obtained by curing a curable composition that does not contain a crystalline polyoxyalkylene polymer.
• the cured product of Comparative Example 2 is obtained by curing a curable composition that contains a crystalline polyoxyalkylene polymer that does not have a reactive silicon group.
• Example 1 Comparing the results of Example 1 and Comparative Example 1, the cured product of Example 1 has higher stresses at 50% elongation and 100% elongation than the cured product of Comparative Example 1, and is stronger at the same elongation rate. In addition, the stress at break is higher than that of the cured product of Comparative Example 1, and it does not break unless a large force is applied. This suggests that the elastic modulus and strength of the cured product are improved by blending a crystalline polyoxyalkylene polymer.
• Example 1 Comparing the results of Example 1 and Comparative Example 1, it is suggested that the effect of adding a crystalline polyoxyalkylene polymer is exhibited because the crystalline polyoxyalkylene polymer has a reactive silicon group.
• the curable composition according to one embodiment of the present invention can be used as a sealant, an adhesive, or the like.

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