Classifications

• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

• the present invention relates to a curable composition containing a reactive silicon group-containing polymer.
• Reactive silicon groups Polymers that have hydroxyl groups or hydrolyzable groups on the silicon atom and have silicon-containing groups that can form siloxane bonds (hereafter referred to as "reactive silicon groups”) are known as moisture-reactive polymers, and are found in many industrial products such as adhesives, sealants, coating materials, paints, and pressure sensitive adhesives, and are used in a wide range of fields.
• Reactive silicon groups include structures in which three hydrolyzable groups are bonded to one silicon atom (e.g., trialkoxysilyl groups), and structures in which two hydrolyzable groups are bonded to one silicon atom (e.g., dialkoxysilyl groups). It is generally known that silicon groups with three hydrolyzable groups are more active and have a faster curing rate than silicon groups with two hydrolyzable groups (see, for example, paragraph [0019] of Patent Document 2).
• patent document 1 proposes a curable composition that uses a combination of a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester polymer.
• polymers with reactive silicon groups are stable over the long term, as the silicon groups do not react even when coexisting with moisture in the absence of a curing catalyst, but the curing reaction proceeds when a curing catalyst is mixed in.
• organotin catalysts with carbon-tin bonds have been widely used as curing catalysts, but there are concerns about the toxicity of organotin catalysts to living organisms, and alternative catalysts are sometimes required.
• Patent Documents 2 and 3 disclose that the use of a combination of a metal alkoxide and ammonium hydroxide as a curing catalyst other than tin significantly increases the curing speed of polymers having reactive silicon groups.
• Patent Documents 2 and 3 When the catalysts disclosed in Patent Documents 2 and 3 are used as curing catalysts for a curable composition containing both a polyoxyalkylene polymer having a reactive silicon group and a (meth)acrylic acid ester polymer having a reactive silicon group, gelling can occur, resulting in problems such as poor appearance of the cured product, variations in surface curing time, failure to cure for a long time, or remaining sticky, and it is desirable to cure in a short time without generating gelling.
• the present invention aims to provide a curable composition that contains a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester polymer, which cures in a short time without using a tin catalyst as a curing catalyst and without generating a gel.
• the present inventors discovered that in a curable composition containing a reactive silicon group-containing polyoxyalkylene polymer, a reactive silicon group-containing (meth)acrylic acid ester polymer, and a specific non-tin catalyst, the polyoxyalkylene polymer has a silicon group with three hydrolyzable groups, and the (meth)acrylic acid ester polymer has a silicon group with two hydrolyzable groups, so that the composition cures in a short time without using a tin catalyst as a curing catalyst and without generating a gel, leading to the present invention.
• the present invention relates to a polyoxyalkylene polymer (A) having a reactive silicon group;
• a curable composition comprising: (B) a (meth)acrylic acid ester polymer having a reactive silicon group; and (C) a curing catalyst,
• the reactive silicon group of the polymer (A) has a structure represented by the following general formula (1), in which three hydrolyzable groups are bonded to one silicon atom:
• the reactive silicon group of the polymer (B) has a structure represented by the following general formula (2), in which two hydrolyzable groups are bonded to one silicon atom:
• each X independently represents a hydrolyzable group.
• -SiR 2 Z 2 (2) In the formula, R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group.
• Each Z independently represents a hydrolyzable group.
• a curable composition containing a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester polymer, which cures in a short time without generating a gel, without using a tin catalyst as a curing catalyst. Furthermore, according to the present invention, it is possible to provide a curable composition which is less prone to thickening over time and has good handleability.
• the curable composition according to the present disclosure contains, as a polymer having a reactive silicon group, both a polyoxyalkylene polymer (A) having a reactive silicon group (hereinafter also referred to as reactive silicon group-containing polyoxyalkylene polymer (A) or polymer (A)) and a (meth)acrylic acid ester polymer (B) having a reactive silicon group (hereinafter also referred to as reactive silicon group-containing (meth)acrylic acid ester polymer (B) or polymer (B)).
• A polyoxyalkylene polymer having a reactive silicon group
• B (meth)acrylic acid ester polymer having a reactive silicon group
• the reactive silicon group in the polymer (A) has a structure in which three hydrolyzable groups are bonded to one silicon atom, and is represented by the general formula (1): -SiX3 (1) In the formula, each X independently represents a hydrolyzable group.
• the curable composition according to the present disclosure can exhibit good curability.
• Examples of X include hydroxyl groups, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups.
• alkoxy groups are more preferred because they are mildly hydrolyzable and easy to handle, with methoxy and ethoxy groups being even more preferred, and methoxy groups being particularly preferred.
• reactive silicon groups represented by general formula (1) include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, and triacetoxysilyl groups.
• trimethoxysilyl triethoxysilyl
• tris(2-propenyloxy)silyl triacetoxysilyl groups.
• trialkoxysilyl groups are preferred, trimethoxysilyl and triethoxysilyl groups are more preferred, and trimethoxysilyl groups are particularly preferred.
• the number of reactive silicon groups in one molecule of polymer (A) is preferably 1 to 7 on average, more preferably 1.1 to 3.4, and particularly preferably 1.2 to 2.6.
• the reactive silicon groups of polymer (A) are present at the ends of the main chain. Since this shows good curability and is likely to exhibit rubber elastic behavior, the number of reactive silicon groups per end of polymer (A) is preferably 0.5 or more on average, more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more.
• a polymer (A) obtained by using a polyoxyalkylene polymer having two or more olefin groups at one main chain end as an intermediate can have an average of more than 1.0 reactive silicon group per end.
• the main chain structure of the polymer (A) may be linear or branched.
• the main chain of the polymer (A) is composed of a repeating unit represented by -R 1 -O- (wherein R 1 is a linear or branched alkylene group having 1 to 14 carbon atoms). R 1 is preferably a linear or branched alkylene group having 2 to 4 carbon atoms.
• repeating unit represented by -R 1 -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 O-, with -CH 2 CH 2 O- and -CH 2 CH(CH 3 )O- being preferred, and -CH 2 CH(CH 3 )O- being more preferred.
• the number average molecular weight of polymer (A) is not particularly limited, but is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, particularly preferably 12,000 to 40,000, and most preferably 13,000 to 30,000, as calculated in terms of polystyrene by GPC measurement.
• the number average molecular weight is within the above range, the amount of reactive silicon groups introduced is appropriate, making it easy to obtain a reactive silicon group-containing polyoxyalkylene polymer (A) with high strength while keeping production costs within an appropriate range.
• the molecular weight of the reactive silicon group-containing polyoxyalkylene polymer (A) can also be expressed as the end group-equivalent molecular weight calculated by directly measuring the end group concentration of the polymer precursor before the introduction of the reactive silicon groups by titration analysis based on the principles of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into account the structure of the polymer (degree of branching determined by the polymerization initiator used).
• the end group-equivalent molecular weight of the polymer (A) can also be calculated by creating a calibration curve of the number average molecular weight determined by general GPC measurement of the polymer precursor and the above end group-equivalent molecular weight, and converting the number average molecular weight determined by GPC of the reactive silicon group-containing polymer into the end group-equivalent molecular weight.
• the molecular weight distribution (Mw/Mn) of the reactive silicon group-containing polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow. Specifically, it 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. If the molecular weight distribution is within the above range, it is preferable from the viewpoints of ease of handling such as workability and adhesiveness.
• the molecular weight distribution of the reactive silicon group-containing polyoxyalkylene polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
• the polymer (A) can be produced by introducing a reactive silicon group into a precursor polymer to which a reactive silicon group can be introduced.
• the polymer (A) can be produced by introducing an olefin group into a polyoxyalkylene polymer (a1) having a hydroxyl group at its terminal, taking advantage of 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 (a1) having a hydroxyl group at the 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 group-terminated polymer with a small molecular weight distribution (Mw/Mn).
• Initiators having a hydroxyl group are not particularly limited, but examples include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polypropylene 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.
• the epoxy compound is not particularly limited, but examples include alkylene oxides such as ethylene oxide, propylene oxide, 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 (a1) having a hydroxyl group at the end, it is preferable to first react an alkali metal salt with the polyoxyalkylene polymer (a1) to convert the terminal hydroxyl group into an alkoxide. Also, a composite metal cyanide complex catalyst can be used instead of the alkali metal salt. In this way, a polyoxyalkylene polymer (a2) having an alkoxide terminal 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 alkoxide-terminated polyoxyalkylene polymer (a2) thus obtained can be converted to a structure containing an olefin group by reacting an electrophilic agent (a3) having an olefin group, thereby forming a polyoxyalkylene polymer (a4) having an olefin group in the terminal structure.
• the electrophile (a3) having an olefin group is not particularly limited as long as it is a compound that can react with the alkoxide terminal of the polyoxyalkylene polymer (a2) and introduce an olefin group into the polyoxyalkylene polymer, but examples of such an electrophile include organic halides (a3-1) having an olefin group.
• organic halides (a3-1) 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 because of 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.
• the polyoxyalkylene polymer (a4) (precursor polymer) having an olefin group in the terminal structure obtained as above is subjected to a hydrosilylation reaction with a hydrosilane compound (a5) having a reactive silicon group, thereby introducing a reactive silicon group into the polymer.
• a hydrosilylation reaction has the advantages of being easily carried out, of being easy to adjust the amount of reactive silicon group introduced, and of having stable physical properties of the resulting polymer.
• hydrosilane compounds (a5) having a reactive silicon group include halosilanes such as trichlorosilane; alkoxysilanes such as trimethoxysilane and triethoxysilane; and isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane.
• the hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction.
• 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 (a6) having a reactive silicon group and an isocyanate group in one molecule is reacted with a polyoxyalkylene polymer (a1) (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 (a6) 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 (a1) and a reactive silicon group in one molecule, but specific examples include (3-isocyanatepropyl)trimethoxysilane, (3-isocyanatepropyl)triethoxysilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)triethoxysilane, 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, may 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 polymer (A) can be applied in which an excess of polyisocyanate compound (a7) is reacted with polyoxyalkylene polymer (a1) having a hydroxyl group at the end to produce a polymer (precursor polymer) having an isocyanate group at the end, and then the precursor polymer is reacted with compound (a8) 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 polyoxyalkylene polymer (A) having a reactive silicon group at the end of the polymer backbone.
• polyisocyanate compound (a7) examples include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.
• aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate
• aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.
• Examples of the compound (a8) having a group that reacts with an isocyanate group and a reactive silicon group include amino group-containing silanes such as ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -(N-phenyl)aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, and N-cyclohexylaminomethyltrimethoxysilane; hydroxy group-containing silanes such as ⁇ -hydroxypropyltrimethoxysilane; and mercapto group-containing silanes such as ⁇ -mercaptopropyltrimethoxysilane.
• a method for producing polymer (A) can be applied in which a compound (a9) having a reactive silicon group and a mercaptan group in one molecule is reacted with a polyoxyalkylene polymer (a4) (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.
• This method can also be used to produce a polyoxyalkylene polymer (A) having a reactive silicon group at the end of the polymer backbone.
• reactive silicon group-containing polyoxyalkylene polymers (A) include Kaneka Silyl (registered trademark) SAX520, SAX530, SAX580, and SAX590 (all manufactured by Kaneka Corporation).
• the curable composition according to the present disclosure can be cured in a short time without producing a gel by combining a reactive silicon group-containing polyoxyalkylene polymer (A) having a structure in which three hydrolyzable groups are bonded to one silicon atom with a reactive silicon group-containing (meth)acrylic acid ester polymer (B) having a structure in which two hydrolyzable groups are bonded to one silicon atom.
• the reactive silicon group in the polymer (B) has a structure in which two hydrolyzable groups are bonded to one silicon atom, and is represented by the general formula (2): -SiR 2 Z 2 (2)
• R2 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group.
• Each Z independently represents a hydrolyzable group.
• R2 is a hydrocarbon group having 1 to 20 carbon atoms.
• the number of carbon atoms in the hydrocarbon group represented by R2 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.
• R2 examples include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group; alkenyl groups such as a vinyl group, a 2-propenyl group, and a 3-butenyl group; cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group; aryl groups such as a phenyl group, a naphthalene-1-yl group, and a naphthalene-2-yl group; and aralkyl groups such as a benzyl group and a phenethyl group.
• alkyl groups such as a
• R2 examples include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups.
• R2 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
• Z examples include hydroxyl groups, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups.
• alkoxy groups are more preferred because they are mildly hydrolyzable and easy to handle, with methoxy and ethoxy groups being even more preferred, and methoxy groups being particularly preferred.
• reactive silicon groups represented by general formula (2) include, but are not limited to, dimethoxymethylsilyl groups, diethoxymethylsilyl groups, and dimethoxyethylsilyl groups.
• dialkoxysilyl groups are preferred, dimethoxysilyl groups are more preferred, and dimethoxymethylsilyl groups are particularly preferred.
• the reactive silicon group represented by general formula (1) in polymer (A) is a trialkoxysilyl group
• the reactive silicon group represented by general formula (2) in polymer (B) is a dialkoxysilyl group
• the alkoxy group in the reactive silicon group in polymer (A) and the alkoxy group in the reactive silicon group in polymer (B) are the same alkoxy group, and it is particularly preferred that both are methoxy groups.
• the reactive silicon group in polymer (A) is a trimethoxysilyl group
• the reactive silicon group in polymer (B) is a dimethoxymethylsilyl group.
• the (meth)acrylic acid ester monomer constituting the main chain of the reactive silicon group-containing (meth)acrylic acid ester polymer (B) is not particularly limited, and various monomers can be used. Specifically, 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, nonaphthalene (meth)acrylate, methyl acrylate, ethyl (meth)acryl
• Other monomer units include, for example, acrylic acids such as acrylic acid and methacrylic acid; amide groups such as N-methylol acrylamide and N-methylol methacrylamide; epoxy groups such as glycidyl acrylate and glycidyl methacrylate; and monomers containing nitrogen-containing groups such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.
• acrylic acids such as acrylic acid and methacrylic acid
• amide groups such as N-methylol acrylamide and N-methylol methacrylamide
• epoxy groups such as glycidyl acrylate and glycidyl methacrylate
• monomers containing nitrogen-containing groups such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.
• the (meth)acrylic acid ester polymer (B) may be a polymer obtained by copolymerizing a (meth)acrylic acid ester monomer with a vinyl monomer copolymerizable therewith, and multiple monomers may be used as copolymerization components.
• (meth)acrylic acid ester-based polymers obtained from the above-mentioned monomers copolymers consisting of styrene-based monomers and (meth)acrylic acid-based monomers are preferred due to their excellent physical properties, (meth)acrylic acid ester-based polymers consisting of acrylic acid ester monomers and methacrylic acid ester monomers are more preferred, and acrylic acid ester-based polymers consisting of acrylic acid ester monomers are particularly preferred.
• the number of reactive silicon groups in polymer (B) is preferably 0.5 to 5.0 on average per molecule, more preferably 1.2 or more from the viewpoint of the mechanical properties of the curable composition when cured, and more preferably 3.0 or less from the viewpoint of the stability of polymer (B).
• the method for introducing a reactive silicon group into a (meth)acrylic acid ester polymer is not particularly limited, and for example, the following methods can be used.
• V group a reactive functional group
• Specific examples include a method of copolymerizing 2-hydroxyethyl acrylate, and then reacting the hydroxyl group with an isocyanate silane having a reactive silicon-containing group, and a method of copolymerizing glycidyl acrylate, and then reacting the epoxy group with an aminosilane compound having a reactive silicon-containing group.
• a method of modifying the terminal functional group of a (meth)acrylic acid ester polymer synthesized by a living radical polymerization method to introduce a reactive silicon group is easy to introduce a functional group into the polymer terminal, and by modifying it, a reactive silicon group can be introduced into the polymer terminal.
• This method can produce a polymer with a small 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 following compounds can be exemplified as silicon compounds that can be used to introduce reactive silicon groups into the (meth)acrylic acid ester polymer (B) using the above method.
• Compounds having a polymerizable unsaturated group and a reactive silicon group that can be used in method (i) include 3-(dimethoxymethylsilyl)propyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, and (diethoxymethylsilyl)methyl (meth)acrylate. From the viewpoint of availability, (dimethoxymethylsilyl)propyl (meth)acrylate is particularly preferred.
• Examples of mercaptosilane compounds having a reactive silicon-containing group that can be used in method (ii) include 3-mercaptopropyldimethoxymethylsilane, (mercaptomethyl)dimethoxymethylsilane, etc.
• Examples of compounds having a reactive silicon group and a functional group that reacts with the V group used in method (iii) include isocyanate silane compounds such as 3-isocyanate propyl dimethoxymethyl silane, isocyanate methyl dimethoxymethyl silane, and isocyanate methyl diethoxymethyl silane; epoxy silane compounds such as 3-glycidoxypropyl dimethoxymethyl silane, glycidoxymethyl dimethoxymethyl silane, and glycidoxymethyl diethoxymethyl silane; and amino silane compounds such as 3-aminopropyl dimethoxymethyl silane, aminomethyl dimethoxymethyl silane, and N-cyclohexyl aminomethyl diethoxymethyl silane.
• isocyanate silane compounds such as 3-isocyanate propyl dimethoxymethyl silane, isocyanate methyl dimethoxymethyl silane, and isocyanate methyl diethoxymethyl silane
• epoxy silane compounds such as 3-glycidoxypropyl dim
• any modification reaction can be used, for example, a method using a compound having a silicon group and a functional group capable of reacting with the reactive end group obtained by polymerization, or a method using a compound having a double bond and a functional group capable of reacting with the reactive end group to introduce a double bond to the polymer end, and then introducing a reactive silicon group by hydrosilylation or the like.
• the number average molecular weight of polymer (B) is not particularly limited, but is preferably 500 to 100,000, more preferably 500 to 50,000, and particularly preferably 1,000 to 30,000, in terms of polystyrene equivalent molecular weight measured by GPC.
• polymer (A) and polymer (B) may each be used alone or in combination of two or more types.
• the curable composition according to the present disclosure contains a specific curing catalyst (C).
• the curing catalyst (C) contains a metal alkoxide (C1) and an ammonium hydroxide (C2), or a metal alkoxide (C3) and an ammonium hydroxide (C4). C1) with ammonium hydroxide (C2).
• the metal of the metal alkoxide (C1) is not particularly limited, but examples thereof include titanium, aluminum, zirconium, zinc, sodium, potassium, lithium, magnesium, boron, etc. These may be used alone or in combination of two or more. Among them, titanium is preferred.
• the alkoxy group contained in the metal alkoxide (C1) can be represented by R 3 -O-, where R 3 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms.
• the substituted or unsubstituted hydrocarbon group represented by R 3 is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, more preferably an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group include saturated or unsaturated hydrocarbon groups.
• 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.
• hydrocarbon group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl.
• 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 3s are present, they may be the same as or different from each other.
• the metal alkoxide (C1) may have a substituent other than the alkoxy group, or a chelating ligand.
• the chelating ligand include ⁇ -diketones and ⁇ -ketoesters. Specific examples of ⁇ -diketones will be described later.
• the titanium alkoxide usable as the metal alkoxide (C1) is represented by the general formula (3): (R 3 -O) n Ti-A 4-n (3)
• R3 is the same group as described above, and represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms.
• n is an integer of 1 to 4.
• A is a chelating ligand.
• Examples of the chelating ligand represented by A include 1-aryl-1,3-butanediones such as 2,4-pentanedione, 2,4-hexanedione, 2,4-pentadecanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-phenyl-1,3-butanedione, and 1-(4-methoxyphenyl)-1,3-butanedione, 1,3-diphenyl-1,3-propanedione, 1,3-bis(2-pyridyl)-1,3-propanedione, and 1,3-bis(4-methoxyphenyl)-1,3-propanedione, 3
• Examples of the diketones include 1,2-diphenyl ether, 1,2-diphenyl ether, and 1,2,3-tetramethyl ether.
• Examples of the diketones include 1,2,3 ... Specifically, 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. When multiple A's are present, they 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 alkoxides represented by general formula (3) include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, and diethoxydibutoxytitanium.
• acetylacetonates include ethoxytitanium, 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).
• the metal alkoxide (C1) other than the titanium alkoxide is not particularly limited, but specific examples include aluminum triisopropoxide, zirconium tetrapropoxide, zinc isopropoxide, sodium methoxide, potassium methoxide, lithium methoxide, magnesium ethoxide, triethyl borate, etc.
• titanium alkoxide is particularly preferred. Only titanium alkoxide may be used, or titanium alkoxide may be used in combination with other metal alkoxides.
• the amount of the metal alkoxide (C1) 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 total of the polymer (A) and the polymer (B).
• ammonium hydroxide (C2) that can be contained in the curing catalyst (C) is preferably represented by the following general formula (4).
• 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, 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, with methyl group, ethyl group, and butyl group being 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 hydroxide (C2) represented by the general formula (4) 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 the ammonium hydroxide (C2) 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 total of the polymer (A) and the polymer (B).
• the content ratio (C1/C2) of the metal alkoxide (C1) and the ammonium hydroxide (C2) may be, for example, in the range of 0.1/1 to 10/1 in terms of molar ratio. From the viewpoint of obtaining good curability, it is preferably 1/1 to 10/1, and more preferably 2/1 to 5/1.
• the curable composition according to the present disclosure may contain either the metal alkoxide (C1) or the ammonium hydroxide (C2), or may contain a reaction product obtained by reacting the metal alkoxide (C1) with the ammonium hydroxide (C2). In either embodiment, the effects of the present invention can be achieved.
• 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 metal alkoxide (C1) to the ammonium hydroxide (C2) in the mixture may be, for example, 0.1 to 100, more preferably 0.2 to 10, and particularly preferably 1 to 5.
• the amount of the reaction product of the metal alkoxide (C1) and ammonium hydroxide (C2) 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 total of the polymer (A) and the polymer (B).
• the curable composition according to the present disclosure comprises a reactive silicon group-containing polyoxyalkylene polymer (A), a reactive silicon group-containing (meth)acrylic acid ester polymer (B), and a curing catalyst (C).
• a polymer other than the polymer (A) or the polymer (B) may be added to the extent that it does not affect the effects of the invention.
• Specific examples of polymers that do not fall under the category of polymer (A) include reactive silicon group-containing polyoxyalkylene polymers having a structure in which two or less hydrolyzable groups are bonded to one silicon atom.
• the amount of addition is preferably from 0 to 50% by weight, more preferably 30% by weight or less, and particularly preferably 10% by weight or less, based on the weight of the polymer (A).
• the polymer not corresponding to the polymer (B) is a reactive silicon group-containing (meth)acrylic acid ester polymer having a structure in which three or one hydrolyzable group is bonded to one silicon atom.
• the amount of addition is preferably from 0 to 50% by weight, more preferably 30% by weight or less, and particularly preferably 10% by weight or less, based on the weight of the polymer (B).
• Additives may be added to the curable composition according to the present disclosure, specifically, other silanol condensation catalysts, fillers, adhesion promoters, plasticizers, solvents, diluents, sagging inhibitors, antioxidants, light stabilizers, UV absorbers, physical property adjusters, tackifier resins, compounds containing epoxy groups, photocurable substances, oxygen curable substances, epoxy resins, and other resins.
• various 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, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.
• silanol condensation catalyst In the present invention, a metal alkoxide (C1) and ammonium hydroxide (C2), or a reaction product thereof, is used as a silanol condensation catalyst for hydrolyzing and condensing the reactive silicon groups of the polymer (A) and the polymer (B).
• C1 and C2 ammonium hydroxide
• other silanol condensation catalysts may be used in combination.
• silanol condensation catalysts include, for example, organotin compounds, metal carboxylates, amine compounds, carboxylic acids, fluorine anion-containing compounds, photoacid generators, and photobase generators.
• 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 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 divalent
• potassium neodecanoate monovalent
• barium neodecanoate divalent
• zirconium neodecanoate tetravalent
• iron oleate divalent
• iron oleate trivalent
• titanium oleate titanium oleate
• vanadium oleate trivalent
• 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.
• 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 the total of polymer (A) and polymer (B).
• 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, calcined 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, calcined 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 above fillers may be used alone or in combination of two or more types.
• 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 the total of polymer (A) and polymer (B).
• 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, particularly preferably 1 to 20 parts by weight, per 100 parts by weight of the total of the polymer (A) and the polymer (B).
• 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 various silane coupling agents such as reaction products of aminosilane and epoxysilane, reaction products of aminosilane and (meth)acrylic group-containing silane, etc. can also be used.
• 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 total of polymer (A) and polymer (B).
• 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, a product 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
• 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 paraffin; 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
• alkylsulfonic acid phenyl esters
• 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 total of polymer (A) and polymer (B). 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 the total of polymer (A) and polymer (B).
• 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.
• antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols.
• 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 the total of polymer (A) and polymer (B).
• 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.
• 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 the total of polymer (A) and polymer (B).
• 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.
• the amount of the 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 total of polymer (A) and polymer (B).
• the curable composition according to the present disclosure may contain a physical property adjuster for adjusting the tensile properties of the cured product to be produced, 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(triethyls
• 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 two or more types may be used in combination.
• 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 total of polymer (A) and polymer (B).
• 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 the total of polymer (A) and polymer (B). If it is less than 2 parts by weight, it is difficult to obtain 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 total of the polymer (A) and the polymer (B).
• 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 total of polymer (A) and polymer (B). 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 the surface from becoming sticky and preventing dirt and dust from adhering 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 the total of polymer (A) and polymer (B), 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 as a curing agent, and the ingredients are mixed with the 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 mixed in advance, 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 methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, or ⁇ -glycidoxypropyltrimethoxysilane.
• partially condensed silane compounds such as Evonik's Dynasylan 6490 can be used preferably from the standpoint of safety and stability.
• the amount of the dehydrating agent, particularly a silicon compound that can react with water such as vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total of polymer (A) and polymer (B).
• the curable composition according to the present disclosure can be used in a wide range of applications, including pressure sensitive adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, waterproof coating materials, mold release agents, vibration isolating materials, vibration damping materials, soundproofing materials, foaming materials, paints, spraying materials, electrical and electronic component materials such as solar cell back surface sealing materials, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for devices, acoustic insulating materials, elastic adhesives, binders, contact type adhesives, spray type sealing materials, crack repair materials, tiling adhesives, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealing materials, dental seals, It can be used for various applications such as sealing materials for joints of exterior materials such as decorative materials, food packaging materials, sizing boards, coating materials, anti-slip coating materials, buffer materials, primers, conductive
• a polyoxyalkylene polymer (A) having a reactive silicon group A curable composition comprising: (B) a (meth)acrylic acid ester polymer having a reactive silicon group; and (C) a curing catalyst,
• the reactive silicon group of the polymer (A) has a structure represented by the following general formula (1), in which three hydrolyzable groups are bonded to one silicon atom:
• the reactive silicon group of the polymer (B) has a structure represented by the following general formula (2), in which two hydrolyzable groups are bonded to one silicon atom:
• each X independently represents a hydrolyzable group.
• -SiR 2 Z 2 (2) (In the formula, R2 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each Z independently represents a hydrolyzable group.)
• [Item 2] 2.
• the metal alkoxide (C1) is a titanium alkoxide.
• [Item 4] 4. The curable composition according to any one of items 1 to 3, wherein the reactive silicon group of the polymer (A) is a trialkoxysilyl group, the reactive silicon group of the polymer (B) is a dialkoxysilyl group, and the alkoxy group of the polymer (A) and the alkoxy group of the polymer (B) are the same.
• [Item 5] The curable composition according to any one of claims 1 to 4, wherein the weight ratio of the polymer (A):the polymer (B) is 95:5 to 5:95.
• [Item 6] The curable composition according to any one of claims 1 to 5, wherein the weight ratio of the polymer (A):the polymer (B) is from 80:20 to 60:40.
• [Item 7] A cured product obtained by curing the curable composition according to any one of claims 1 to 6.
• the number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.
• Liquid delivery system Tosoh HLC-8220GPC Column: Tosoh TSKgel Super H series Solvent: THF Molecular weight: polystyrene equivalent Measurement temperature: 40°C
• polymer (A-1) having a number average molecular weight of about 15,800 and having trimethoxysilyl groups at the terminals. It was found that polymer (A-1) had an average of 0.8 trimethoxysilyl groups at one terminal and an average of 1.6 trimethoxysilyl groups per molecule.
• polymer (A-2) having a number average molecular weight of 28,500 and trimethoxysilyl groups at the terminals. It was found that polymer (A-2) had an average of 0.8 trimethoxysilyl groups at one terminal and an average of 1.6 trimethoxysilyl groups per molecule.
• polymer (A-3) having a number average molecular weight of about 16,400 and trimethoxysilyl groups at the terminals. It was found that polymer (A-3) had an average of 0.7 trimethoxysilyl groups at one terminal and an average of 2.2 trimethoxysilyl groups per molecule.
• the obtained unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation, and the metal salts in the polymer were removed by devolatilizing the hexane from the obtained hexane solution under reduced pressure.
• polyoxypropylene (Q-4) having a plurality of carbon-carbon unsaturated bonds at the terminals was obtained.
• 500 g of the obtained polymer (Q-4) was added with 50 ⁇ L of a platinum divinyldisiloxane complex solution (a 3 wt % isopropanol solution calculated as platinum), and 9.6 g of trimethoxysilane was slowly added dropwise while stirring.
• the mixed solution was reacted at 90° C. for 2 hours, and then unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-4) having multiple trimethoxysilyl groups at its terminals and a number average molecular weight of 28,000. It was found that the polymer (A-4) had an average of 1.7 trimethoxysilyl groups at one terminal and an average of 3.4 trimethoxysilyl groups per molecule.
• the reaction product was obtained by distilling off isopropanol and methanol at a pressure of 10 mmHg (10 mmHg), to obtain 80 g of the reaction product. Further, 25 g of isopropanol was added to obtain 105 g of catalyst (C-1) as a transparent liquid.
• Example 1 70 parts by weight of the polymer (A-1) obtained in Synthesis Example 1 was mixed with 30 parts by weight of the polymer (B-1) obtained in Synthesis Example 6, 50 parts by weight of PPG2000 (manufactured by Mitsui Fine Chemicals, Inc.), and 250 parts by weight of Carbital 110S (manufactured by IMERYS Carbonates: heavy calcium carbonate) to uniformly disperse.
• PPG2000 manufactured by Mitsui Fine Chemicals, Inc.
• Carbital 110S manufactured by IMERYS Carbonates: heavy calcium carbonate
• the obtained curable composition was filled into a mold about 5 mm thick with a spatula under conditions of 23°C and 50% relative humidity, and the time when the surface was smoothed to a flat shape was defined as the curing start time.
• the time from the curing start time to the time when the composition no longer adhered to the spatula when the surface was touched with the spatula was defined as the skinning time.
• the obtained curable composition was aged for 7 days after preparation under conditions of 23° C. and a relative humidity of 50% RH, and then the viscosity at 10 rpm was measured using a BS type viscometer with rotor No. 7 manufactured by Toki Sangyo Co., Ltd.
• Example 2 Except for changing the polymer (A-1) to the polymer (A-2), the same evaluation as in Example 1 was carried out. The results are shown in Table 1.
• Example 2 The evaluation was carried out in the same manner as in Example 2, except that the polymer (B-1) was changed to the polymer (B'-1). The results are shown in Table 1.
• Example 3 Except for changing the polymer (A-1) to the polymer (A-3), the same evaluation as in Example 1 was carried out. The results are shown in Table 1.
• Example 4 Except for changing the polymer (A-1) to the polymer (A-4), the same evaluation as in Example 1 was carried out. The results are shown in Table 1.
• Example 5 Except for changing the polymer (A-1) to the polymer (A-5), the same evaluation as in Example 1 was carried out. The results are shown in Table 1.
• Example 6 The evaluation was carried out in the same manner as in Example 1, except that the blending amount of the polymer (A-1) was changed to 80 parts by weight and the blending amount of the polymer (B-1) was changed to 20 parts by weight. The results are shown in Table 1.
• Example 7 The evaluation was carried out in the same manner as in Example 1, except that the blending amount of the polymer (A-1) was changed to 60 parts by weight and the blending amount of the polymer (B-1) was changed to 40 parts by weight. The results are shown in Table 1.
• Example 8 Except for changing the polymer (B-1) to the polymer (B-2), the same evaluation as in Example 1 was carried out. The results are shown in Table 1.
• Example 9 The same evaluation as in Example 1 was carried out, except that 1 part by weight of Tinuvin 770 (manufactured by BASF Japan Ltd.: hindered amine-based light stabilizer), 1 part by weight of Tinuvin 326 (manufactured by BASF Japan Ltd.: benzotriazole-based ultraviolet absorber), and 1.2 parts by weight of Irganox 245 (manufactured by BASF: hindered phenol-based antioxidant) were added. The results are shown in Table 1.
• Comparative Example 6 The same evaluation as in Comparative Example 1 was carried out, except that 1 part by weight of Tinuvin 770 (manufactured by BASF Japan Ltd.: hindered amine-based light stabilizer), 1 part by weight of Tinuvin 326 (manufactured by BASF Japan Ltd.: benzotriazole-based ultraviolet absorber), and 1.2 parts by weight of Irganox 245 (manufactured by BASF Ltd.: hindered phenol-based antioxidant) were added. The results are shown in Table 1.
• Example 1 The same evaluation as in Example 1 was carried out, except that 3 parts by weight of the catalyst (C-1) was changed to 0.2 parts by weight of a tin catalyst, Neostan S-1 (dioctyltin bis(triethoxysilicate) manufactured by Nitto Kasei Co., Ltd.). The results are shown in Table 1.
• Example 1 which contains a polyoxyalkylene polymer (A) having a silicon atom bonded to three hydrolyzable groups, a (meth)acrylic ester polymer (B) having a silicon atom bonded to two hydrolyzable groups, and a curing catalyst (C) containing a reaction product of a metal alkoxide and ammonium hydroxide, has a shorter skinning time and no gel formation on the liquid surface, and can be applied smoothly, compared to Comparative Example 1, which contains a (meth)acrylic ester polymer having a silicon atom bonded to three hydrolyzable groups instead of polymer (B). All of the products that could be applied smoothly maintained a state of no gel formation even after curing.
• Example 1 as compared with Comparative Example 1, suppresses the increase in viscosity over time after one week has passed, and is excellent in handleability.
• Example 1 shows that, in comparison with Comparative Example 1, although it exhibits rapid curing properties, the generation of gel and thickening over time are suppressed.
• Example 2 and Comparative Example 2 Example 3 and Comparative Example 3, Example 4 and Comparative Example 4, Example 5 and Comparative Example 5, and Example 9 and Comparative Example 6.
• Reference Examples 1 and 2 are systems that use a tin catalyst as the curing catalyst.
• Reference Example 1 which uses a (meth)acrylic acid ester polymer (B) having a silicon atom bonded to two hydrolyzable groups, has a longer skinning time and lower curing properties than Reference Example 2, which uses a (meth)acrylic acid ester polymer having a silicon atom bonded to three hydrolyzable groups.
• Reference Example 2 which uses a (meth)acrylic acid ester polymer having a silicon atom bonded to three hydrolyzable groups.

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