Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/057—Metal alcoholates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • 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
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • 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

Definitions

• the present invention relates to a curable composition containing an organic polymer having a silicon group (hereinafter also referred to as a "reactive silicon group”) that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and that can form a crosslink by forming a siloxane bond, and a method for producing the same.
• a reactive silicon group an organic polymer having a silicon group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and that can form a crosslink by forming a siloxane bond
• Organic polymers with reactive silicon groups are known to have the property of crosslinking through the formation of siloxane bonds accompanied by hydrolysis of silyl groups due to moisture, etc., even at room temperature, resulting in a rubber-like cured product.
• Such organic polymers with reactive silicon groups are already being produced industrially, and are widely used in applications such as sealants, adhesives, paints, and waterproofing materials.
• curable compositions containing organic polymers with reactive silicon groups usually contain a curing catalyst (also called a silanol condensation catalyst) such as an organotin compound with a carbon-tin bond, such as dibutyltin bis(acetylacetonate).
• a curing catalyst also called a silanol condensation catalyst
• organotin compound with a carbon-tin bond such as dibutyltin bis(acetylacetonate
• Patent Document 1 describes the combined use of a titanium compound having a specific structure, a secondary or tertiary amine, and an organic acid such as neodecanoic acid as a curing catalyst for organic polymers having reactive silicon groups.
• Patent Document 1 discloses a non-organotin curing catalyst with good curing properties, but the curing properties do not necessarily reach a sufficient level, and there is a need to improve them.
• the present invention aims to provide a curable composition that contains a reactive silicon group-containing organic polymer and a non-organotin curing catalyst and exhibits improved curability.
• the inventors discovered that by forming a curing catalyst from a carboxylic acid compound, an amine compound with a specific structure, and a metal compound with a specific structure, the curing properties of a curable composition containing a reactive silicon group-containing organic polymer are improved, and thus the present invention was completed.
• the present invention relates to a compound represented by the following general formula (1): -SiR 1 3-a X a (1)
• R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by R 0 3 SiO-.
• the three R 0 's may be the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms.
• X represents a hydroxyl group or a hydrolyzable group.
• a represents 1, 2, or 3.
• a curable composition comprising an organic polymer (A) having a reactive silicon group represented by the formula: the curing catalyst (B) comprises a carboxylic acid compound (b1), a cyclic secondary amine compound (b2) having an ester group, and a metal compound (b3);
• the metal compound (b3) is represented by the following general formula (2): M (OR 2 ) d Y ed (2) (In the formula, M represents a metal atom having a valence e selected from the group consisting of titanium metal, aluminum metal, zirconium metal, and hafnium metal. e represents the valence of the central metal.
• R2 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
• Y represents a chelate coordination compound.
• d represents 0 or an integer from 1 to e.
• the present invention provides a curable composition that contains a reactive silicon group-containing organic polymer and a non-organotin curing catalyst and exhibits improved curability.
• the reactive silicon group-containing organic polymer (A) has a polymer skeleton (also called a main chain structure) and a polymer chain end bonded to the polymer skeleton.
• the polymer skeleton is a structure in which a plurality of monomer units are continuously formed by bonding a plurality of monomers by polymerization, condensation, etc.
• the monomer may be one type, or a mixture of a plurality of types may be bonded.
• the polymer chain end refers to the portion located at the end of the reactive silicon group-containing organic polymer (A).
• the number of polymer chain ends of the reactive silicon group-containing organic polymer (A) is 2 when the polymer skeleton is entirely linear, and is 3 or more when the polymer skeleton is entirely branched. In addition, when the polymer skeleton is a mixture of linear and branched chains, the number can be between 2 and 3 on average.
• the reactive silicon groups of the organic polymer (A) may be present in the polymer backbone and/or at the polymer chain end. Two or more reactive silicon groups may also be present at one polymer chain end.
• the curable composition according to the present disclosure is used as an adhesive, a sealant, an elastic coating agent, a pressure sensitive adhesive, or the like, it is preferable that the reactive silicon groups are contained at the polymer chain end of the organic polymer (A).
• the organic polymer (A) has a reactive silicon group represented by the following general formula (1). -SiR 1 3-a X a (1)
• R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by R 0 3 SiO-.
• the three R 0 's may be the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms.
• X represents a hydroxyl group or a hydrolyzable group.
• a represents 1, 2, or 3. When a plurality of R 1's or X's are present, they may be the same or different.
• R 1 in the general formula (1) examples include alkyl groups such as methyl and ethyl groups; alkyl groups having a hetero-containing group such as chloromethyl, methoxymethyl, and 3,3,3-trifluoropropyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; aralkyl groups such as benzyl; and triorganosiloxy groups represented by R 0 3 SiO-, where R 0 is a methyl group, phenyl group, or the like.
• alkyl groups or alkyl groups having a hetero-containing group more preferably methyl, ethyl, chloromethyl, and methoxymethyl groups, even more preferably methyl and ethyl groups, and particularly preferably methyl groups.
• R 1 When there are a plurality of R 1 , they may be the same as or different from each other.
• X in general formula (1) represents a hydroxyl group or a hydrolyzable group.
• the hydrolyzable group is not particularly limited and may be a known hydrolyzable group, such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
• an alkoxy group, an acyloxy group, a ketoximate group, and an alkenyloxy group are preferred.
• an alkoxy group is more preferred, a methoxy group and an ethoxy group are even more preferred, and a methoxy group is particularly preferred.
• Xs there are multiple Xs, they may be the same or different from each other.
• a is 1, 2, or 3. a is preferably 2 or 3. From the viewpoint of better curability, a is particularly preferably 3.
• the reactive silicon group represented by the general formula (1) is not particularly limited, but examples thereof include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, dimethoxyphenylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, and (N,N-diethylaminomethyl)diethoxysilyl group.
• the dimethoxymethylsilyl group and the trimethoxysilyl group are preferred because they are easy to synthesize.
• the trimethoxysilyl group and the methoxymethyldimethoxysilyl group are preferred because they provide high curing properties.
• the trimethoxysilyl group and the triethoxysilyl group are preferred because they provide a cured product that exhibits a high recovery rate and low water absorption.
• the main chain structure (also referred to as polymer skeleton) of the reactive silicon group-containing organic polymer (A) is not particularly limited, and various main chain structures can be used.
• polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyolefins obtained by condensation of dibasic acids such as adipic acid with glycols, or ring-opening polymerization of lactones; Examples of such polymers include ester polymers, (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl
• saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have relatively low glass transition temperatures and the resulting cured products have excellent cold resistance. Only one of these may be used, or two or more may be used in combination.
• Polyoxyalkylene polymers and (meth)acrylic acid ester polymers are particularly preferred because they have high moisture permeability, excellent deep curing properties when made into a one-component curable composition, and excellent adhesion. Polyoxyalkylene polymers are more preferred, and polyoxypropylene is even more preferred.
• (Meth)acrylic acid ester polymers are useful because by combining various monomer compositions that make up the polymer, it is possible to obtain effects such as improving adhesion, improving heat resistance and weather resistance, and reducing the water absorption of the cured product obtained by curing the curable composition.
• the polyoxyalkylene polymer is preferably a polymer having a repeating unit represented by -R-O- (wherein R is a linear or branched alkylene group having 1 to 14 carbon atoms). It is more preferable that R is a linear or branched alkylene group having 2 to 4 carbon atoms.
• R is a linear or branched alkylene group having 2 to 4 carbon atoms.
• Specific examples of the repeating unit represented by -R-O- include -CH 2 O-, -CH 2 CH 2 O-, -CH 2 CH(CH 3 ) O-, -CH 2 CH(C 2 H 5 )O-, -CH 2 C(CH 3 )(CH 3 )O-, and -CH 2 CH 2 CH 2 CH 2 O-.
• the main chain structure of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
• a polyoxypropylene-based polymer having oxypropylene repeat units in an amount of 50% by weight or more, more preferably 80% by weight or more, of the polymer main chain structure is preferred because it is amorphous and has a relatively low viscosity.
• the main chain structure of the polyoxyalkylene polymer may be linear or may have a branched chain.
• the number of branches is preferably 1 to 6 (i.e., the number of terminal hydroxyl groups is 3 to 8), more preferably 1 to 4 (i.e., the number of terminal hydroxyl groups is 3 to 6), and most preferably 1 (i.e., the number of terminal hydroxyl groups is 3).
• the polymer has a branched chain and the reactive silicon group is a trimethoxysilyl group, it is possible to obtain a cured product with a particularly low water absorption rate.
• the polyoxyalkylene polymer is preferably one obtained by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator.
• cyclic ether compounds examples include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among the cyclic ether compounds, it is particularly preferable to use propylene oxide, since it gives an amorphous polyether polymer with a relatively low viscosity.
• initiators include alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol; and hydroxyl-terminated polyoxyalkylene polymers having a number average molecular weight of 300 to 4,000, such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.
• alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glyco
• Methods for synthesizing polyoxyalkylene polymers include, but are not limited to, a polymerization method using an alkaline catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst such as the complex obtained by reacting an organoaluminum compound with porphyrin as shown in JP-A-61-215623, a polymerization method using a composite metal cyanide complex catalyst as shown in JP-B-46-27250, JP-B-59-15336, U.S. Pat. No. 3,278,457, U.S. Pat. No. 3,278,458, U.S. Pat. No. 3,278,459, U.S. Pat. No. 3,427,256, U.S. Pat.
• a polyoxyalkylene polymer containing other bonds such as urethane bonds and urea bonds in the main chain structure may be used as long as it does not significantly impair the effects of the invention.
• a specific example of such a polymer is a polyurethane prepolymer.
• Polyurethane prepolymers can be obtained by known methods, for example, by reacting a polyol compound with a polyisocyanate compound.
• polyol compounds include polyether polyols, polyester polyols, polycarbonate polyols, and polyether polyester polyols.
• polyisocyanate compound examples include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, and hexamethylene diisocyanate.
• the polyurethane prepolymer may be one having either a hydroxyl group or an isocyanate group at the end.
• the reactive silicon group-containing organic polymer (A) is a polyoxyalkylene polymer that does not contain a urethane bond, a urea bond, an ester bond, or an amide bond in the main chain structure.
• the reactive silicon group-containing organic polymer (A) is preferably obtained by introducing reactive silicon groups into a polymer by any one of the following methods (a) to (d).
• examples of the terminal carbon-carbon unsaturated group include a vinyl group, an allyl group, a methallyl group, an allenyl group, and a propargyl group.
• the reactive silicon group-containing organic polymer (A) obtained using a silane compound in which W is a methylene group is preferred in that it exhibits extremely high curability.
• Method (a) is preferred because it tends to give a reactive silicon group-containing organic polymer (A) with good storage stability.
• Methods (b), (c) and (d) are preferred because they give a high conversion rate in a relatively short reaction time.
• Examples include those proposed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, and JP-A-61-218632, which introduce reactive silicon groups by hydrosilylation or the like into polyoxypropylene polymers with a high molecular weight and narrow molecular weight distribution, with a number average molecular weight of 6,000 or more and Mw/Mn of 1.6 or less, and those proposed in JP-A-3-72527.
• the molecular weight distribution (Mw/Mn) of the reactive silicon group-containing organic polymer (A) is not particularly limited, but is preferably 1.6 or less, more preferably 1.5 or less, and particularly preferably 1.4 or less. From the viewpoint of improving various mechanical properties such as durability and elongation of the cured product, a molecular weight distribution of 1.2 or less is preferable.
• the number average molecular weight of the reactive silicon group-containing organic polymer (A), as calculated as polystyrene equivalent molecular weight by GPC, is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 8,000 to 35,000.
• the mechanical properties of the cured product are excellent, and since the amount of reactive silicon groups introduced is appropriate, it is possible to obtain an organic polymer (A) that exhibits good curability, has a manageable viscosity, and is excellent in workability while keeping production costs within an appropriate range.
• the molecular weight of the reactive silicon group-containing organic polymer (A) can also be expressed as the end group molecular weight calculated by directly measuring the end group concentration using titration analysis based on the principles of the hydroxyl value measurement method in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into account the structure of the organic polymer (degree of branching determined by the polymerization initiator used).
• the end group converted molecular weight of the organic polymer (A) can also be calculated by creating a calibration curve of the number average molecular weight calculated by general GPC measurement of the polymer precursor and the above end group converted molecular weight, and converting the number average molecular weight calculated by GPC of the organic polymer (A) into the end group converted molecular weight.
• the reactive silicon groups of the organic polymer (A) are present at the polymer chain end. Since this shows good curability and is likely to exhibit rubber elastic behavior, the number of reactive silicon groups per polymer chain end of the organic 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.
• the number of polymer chain ends per molecule of the organic polymer (A) is preferably 2 to 8, more preferably 2 to 4, and particularly preferably 2 or 3.
• the number of reactive silicon groups in one molecule of the organic polymer (A) is preferably from 1 to 7 on average, more preferably from 1 to 3.4, and particularly preferably from 1 to 2.6.
• the reactive silicon group-containing organic polymer (A) When the reactive silicon group-containing organic polymer (A) is branched, the reactive silicon group may be at the end of the main chain of the organic polymer, at the end of a side chain (branched chain), or both. In particular, when the reactive silicon group is at the end of the main chain, the molecular weight between crosslinking points becomes longer, which is preferable because it makes it easier to obtain a rubber-like cured product that has high strength, high elongation, and a low elastic modulus.
• an organic polymer having two or more carbon-carbon unsaturated bonds at one polymer chain end is used, and the organic polymer (A) obtained by the above methods (a) and (c) has two or more reactive silicon groups at one polymer chain end.
• Such an organic polymer (A) exhibits high curability, and the obtained cured product is expected to have high strength and high recovery.
• reactive silicon group-containing organic polymers (A) include various reactive silicon group-containing polyoxypropylene products under the trade names Kaneka MS Polymer or Kaneka Silyl, Kaneka TA Polymer, Kaneka XMAP, and other reactive silicon group-containing poly(meth)acrylic acid esters, and Kaneka EPION, and other reactive silicon group-containing polyisobutylenes.
• the curable composition according to the present disclosure contains a curing catalyst (B) used to form a cured product by hydrolyzing and condensing the reactive silicon groups contained in the organic polymer (A).
• the curing catalyst (B) contains three catalyst components in order to improve the curability of the curable composition: a carboxylic acid compound (b1), a cyclic secondary amine compound (b2) having an ester group, and a metal compound (b3).
• the curing catalyst (B) may be a mixture of (b1), (b2), and (b3).
• (b1), (b2), and (b3) may not react or bond with each other, and may be included as independent components.
• any two or all three of (b1), (b2), and (b3) may react with each other and bond with each other.
• the carboxylic acid compound (b1) may be, for example, a compound having one or more (preferably one) carboxyl groups (-COOH) in one molecule and having 1 to 30 (preferably 2 to 20, more preferably 6 to 12) carbon atoms.
• carboxylic acid compound (b1) examples are not particularly limited, and examples of the aliphatic monocarboxylic acid include linear saturated fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, and tridecylic acid; monoene unsaturated fatty acids such as acrylic acid and methacrylic acid; polyene unsaturated fatty acids; 2-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2 -Diethylbutyric acid, 2-phenylbutyric acid, isovaleric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, octylic acid
• Aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid and salicylic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid; and halogen-substituted aromatic carboxylic acids such as chlorobenzoic acid.
• carboxylic acid derivatives that produce carboxylic acids upon hydrolysis such as carboxylic acid anhydrides, esters, amides, nitriles, and acyl chlorides, can also be used.
• carboxylic acid compound (b1) 2-ethylhexanoic acid, neononanoic acid, and neodecanoic acid are preferred because they are easily available, inexpensive, and have good compatibility with the reactive silicon group-containing organic polymer (A). Neodecanoic acid is particularly preferred because it is easy to obtain high catalytic activity.
• carboxylic acid compound (b1) one type of compound may be used, or multiple compounds may be used in combination.
• the cyclic secondary amine compound (b2) having an ester group refers to a compound having a cyclic secondary amine skeleton and an ester group.
• the cyclic secondary amine refers to a heterocyclic amine compound having an NH group.
• heterocyclic amine compounds having an NH group include, but are not limited to, non-aromatic heterocyclic amines such as pyrrolidine, piperidine, piperazine, morpholine, and hexamethyleneimine.
• pyrrolidine, piperidine, and hexamethyleneimine are preferred, piperidine and hexamethyleneimine are more preferred, and piperidine is particularly preferred.
• the nitrogen atom of the amine compound may or may not have a substituent, but it is preferable that it does not have one.
• the cyclic secondary amine compound (b2) having an ester group is preferably a compound having an NH group.
• the cyclic secondary amine compound (b2) having an ester group can be represented, for example, by the following general formula (3).
• R 3 -C( O)-O-R 4 (3)
• R 3 represents a cyclic secondary amine skeleton-containing group
• R 4 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
• the cyclic secondary amine skeleton-containing group represented by R3 is not particularly limited as long as it is a group containing a cyclic secondary amine skeleton. However, it is preferable that an atom other than the nitrogen atom contained in the cyclic secondary amine (particularly a carbon atom constituting the ring of the cyclic secondary amine) is bonded to the ester group in formula (3) or (4).
• the cyclic secondary amine skeleton may or may not have a substituent other than the ester group on the ring. Examples of the substituent include a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an amino group, etc.
• the number of carbon atoms in the hydrocarbon group represented by R4 is 1 to 20, preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
• the hydrocarbon group may be aliphatic, alicyclic, or aromatic, but is preferably aliphatic.
• the hydrocarbon group may or may not have a substituent such as a halogen atom, a hydroxyl group, or an amino group.
• the molecular weight of the cyclic secondary amine compound (b2) having an ester group is not particularly limited, but may be, for example, about 100 to 1,000. It may also be 120 to 500, or 150 to 200.
• cyclic secondary amine compound (b2) having an ester group examples include ester compounds of piperidine carboxylic acid such as 4-piperidine carboxylic acid, 2-piperidine carboxylic acid, and 3-piperidine carboxylic acid, and ester compounds of pyrrolidine carboxylic acid such as 2-pyrrolidine carboxylic acid.
• ester compounds include methyl esters, ethyl esters, and propyl esters, with ethyl esters being particularly preferred from the viewpoint of curability.
• ester compounds of piperidine carboxylic acid are preferred, ester compounds of 4-piperidine carboxylic acid are more preferred, methyl 4-piperidine carboxylate and ethyl 4-piperidine carboxylate are even more preferred, and ethyl 4-piperidine carboxylate is particularly preferred.
• the cyclic secondary amine compound (b2) having an ester group one type of compound may be used, or multiple compounds may be used in combination.
• Metal compound (b3) is a compound represented by the following general formula (2).
• M represents a metal atom having a valence of e selected from the group consisting of titanium metal, aluminum metal, zirconium metal, and hafnium metal.
• e represents the valence of the central metal.
• R2 represents a substituent. or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
• Y represents a chelate coordination compound.
• d represents 0 or an integer of 1 to e.
• the substituted or unsubstituted hydrocarbon group represented by R2 is preferably an aliphatic or aromatic hydrocarbon group, and is 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 preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
• Examples of the hydrocarbon group represented by R2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl.
• Examples of the substituent that the hydrocarbon group may have include a methoxy group, an ethoxy group, a hydroxyl group, and an acetoxy group. When a plurality of R2s are present, they may be the same or different.
• the chelate coordination compound represented by Y may be a known compound known to coordinate with titanium, aluminum, zirconium, or hafnium.
• examples thereof 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, and 3-benzyl
• the diketones include 2,4-pentanedione, ketoesters such as methyl aceto
• e represents the valence of the central metal
• d represents 0 or an integer from 1 to e. Since the curable composition according to the present disclosure can exhibit better curability, e-d preferably represents an integer from 1 to 4, more preferably an integer from 1 to 3, and particularly preferably represents 2.
• metal compounds (b3) include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium, ethoxytriisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxydibutoxy
• titanium compounds or aluminum compounds are preferred.
• a titanium compound containing a chelate coordination compound represented by Y is preferred, since better curability can be achieved.
• titanium compounds in terms of improving curing properties, tetraisopropoxytitanium, tetrabutoxytitanium, tetra-tert-butoxytitanium, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), and diisobutoxytitanium bis(ethylacetoacetate) are preferred, with diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), and diisobutoxytitanium bis(ethylacetoacetate) being particularly preferred.
• aluminum trialkoxides are preferred from the viewpoint of improving curability, and triisopropoxyaluminum, tri-tert-butoxyaluminum, tri-sec-butoxyaluminum, and tri-n-butoxyaluminum are more preferred.
• the metal compound (b3) one type may be used alone, or two or more types may be used in combination.
• Titanium compounds corresponding to metal compound (b3) have a tendency to easily become colored, and therefore in applications requiring transparency or whiteness, it is preferable that the content is small.
• the content of titanium compounds corresponding to metal compound (b3) is preferably 0.1 parts by weight or less, more preferably 0.05 parts by weight or less, and even more preferably 0.01 parts by weight or less, per 100 parts by weight of organic polymer (A). It is also more preferable that no titanium compounds are contained.
• the carboxylic acid compound (b1), the cyclic secondary amine compound (b2) having an ester group, and the metal compound (b3) may be added and mixed individually with the organic polymer (A) or a mixture of (b1) to (b3) without reacting them in advance.
• the carboxylic acid compound (b1) and the metal compound (b3) may be added and mixed individually with the organic polymer (A) or a mixture of (b1) to (b3) without reacting them in advance.
• a part or all of (b1) to (b3) may be reacted in advance and then added to the organic polymer (A).
• (b1) and (b2) may be reacted, and then the reactant and (b3) may be added to the organic polymer (A) separately or in combination.
• the carboxylic acid compound (b1) and the cyclic secondary amine compound (b2) having an ester group among the above catalyst components are mixed, a carboxylic acid amine complex is formed, and such a complex may be added.
• the mixture will be liquid at room temperature and have good workability.
• a carboxylic acid compound (b1) when a carboxylic acid compound (b1) is reacted with a metal compound (b3), a ligand on the metal and the carboxylic acid (b1) may undergo ligand exchange to form a carboxylic acid metal salt.
• a carboxylic acid metal salt may or may not be added.
• the catalyst it is preferable to appropriately select whether to use the catalyst alone, in a mixture, or in the form of a reactant, depending on the properties of each catalyst component and the combination of multiple catalyst components.
• the reactant any components that become liberated by ligand exchange or the like may be removed.
• each component is liquid under the conditions of use, it is preferable from the standpoint of workability to add them separately when preparing the curable composition.
• the catalyst component is solid, it can be liquefied with a solvent or the like before use, but it may also be possible to liquefy two or more components by mixing or reacting them, which is preferable.
• the total content of the curing catalyst (B) can be appropriately determined taking into consideration the desired curability and the workability of the curable composition, but for example, it may be about 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 1 to 8 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).
• the ratio of the carboxylic acid compound (b1) to the cyclic secondary amine compound (b2) having an ester group can be set appropriately, but the molar ratio of (b1):(b2) may be, for example, about 0.1:1 to 10:1, and from the viewpoint of curability, 0.2:1 to 8:1 is preferred, and 0.5:1 to 5:1 is more preferred.
• the weight ratio of (b1):(b2) may be, for example, about 0.1:1 to 20:1, and from the viewpoint of curability, 0.5:1 to 10:1 is preferred, 1:1 to 8:1 is more preferred, and 2:1 to 6:1 is particularly preferred.
• the ratio of the carboxylic acid compound (b1) to the metal compound (b3) can also be set appropriately, but the molar ratio of (b1):(b3) may be, for example, about 0.1:1 to 10:1, and from the viewpoint of curability, 1:1 to 6:1 is preferred, and 2:1 to 5:1 is more preferred.
• the weight ratio of (b1):(b3) may be, for example, about 0.1:1 to 20:1, and from the viewpoint of curability, 0.5:1 to 10:1 is preferred, 1:1 to 8:1 is more preferred, and 2:1 to 6:1 is particularly preferred.
• the curable composition according to the present disclosure may contain a curing catalyst other than the curing catalyst (B).
• a curing catalyst include organotin compounds, metal salts of carboxylates, amine compounds other than the cyclic secondary amine compound (b2) having an ester group, carboxylic acids, metal alkoxides other than the metal compound (b3), and inorganic acids.
• the content of the curing catalyst other than the curing catalyst (B) is not particularly limited and may be set appropriately, but may be, for example, 0 to 10 parts by weight, 0 to 5 parts by weight, 0 to 3 parts by weight, or 0 to 1 part by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).
• the curable composition according to the present disclosure may contain a silane compound (C) having a hydrolyzable silicon group and an amino group and a molecular weight of 100 to 1500.
• the curable composition may further contain a silane compound (D) having a hydrolyzable silicon group and no amino group and a molecular weight of 100 to 1500.
• the curable composition may contain both the silane compound (C) and the silane compound (D). These silane compounds are also called silane coupling agents.
• the adhesiveness of the curable composition to various substrates can be improved.
• an amino group-free silane compound (D) By adding an amino group-free silane compound (D), the adhesiveness to various substrates can be further improved and the storage stability of the curable composition can be improved.
• the hydrolyzable silicon group contained in the amino group-containing silane compound (C) and the amino group-free silane compound (D) refers to a silicon atom-containing group to which a hydrolyzable group is bonded, and can also be represented by the general formula (1) described above for the reactive silicon group contained in the organic polymer (A).
• the hydrolyzable group contained in the hydrolyzable silicon group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, etc.
• alkoxy groups such as a methoxy group and an ethoxy group are more preferred, and a methoxy group and an ethoxy group are particularly preferred, because they are mildly hydrolyzable and easy to handle.
• the number of hydrolyzable groups bonded to silicon atoms in the amino group-containing silane compound (C) or the amino group-free silane compound (D) may be preferably 3 in order to ensure good adhesion, and may be preferably 2 in order to ensure storage stability of the curable composition.
• the molecular weight of the amino group-containing silane compound (C) or the amino group-free silane compound (D) may be within the range of 100 to 1,500.
• the lower limit of the molecular weight may be 150 or more.
• the upper limit may be 1,000 or less, or 500 or less.
• the amino group-containing silane compound (C) is a compound having a hydrolyzable silicon group and a substituted or unsubstituted amino group, and is sometimes called an aminosilane. It has been used as an adhesion imparting agent in curable compositions containing reactive silicon group-containing organic polymers.
• the substituents of the substituted amino group are not particularly limited, and examples thereof include alkyl groups, aralkyl groups, and aryl groups.
• amino group-containing silane compounds (C) include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriethoxysilane, ⁇ -(2-aminoethyl)aminopropylmethyldiethoxysilane, ⁇ -(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane, ⁇ -(6-aminohexyl)aminopropyltrimethoxysilane,
• the amino group-containing silane compound (C) is preferably ⁇ -aminopropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, or ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane.
• Silane coupling agents in which hydrolyzable silicon groups are partially condensed to form oligomers can be used favorably in terms of safety and stability.
• the silane coupling agents to be condensed may be of one type or multiple types. Examples of oligomerized silane coupling agents include Dynasylan 1146 from Evonik.
• the silane compound (D) having a hydrolyzable silicon group and no amino group may be a compound having a hydrolyzable silicon group and a reactive group other than an amino group, or may be a compound having no reactive groups other than a hydrolyzable silicon group.
• non-amino group-containing silane compound (D) examples include epoxy group-containing silanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane; Isocyanate group-containing silanes such as ⁇ -isocyanate propyl trimethoxy silane, ⁇ -isocyanate propyl triethoxy silane, ⁇ -isocyanate propyl methyl diethoxy silane, ⁇ -isocyanate propyl methyl dimethoxy silane, (isocyanate methyl) trimethoxy silane, and (isocyanate methyl) dimethoxy silane;
• the non-amino group-containing silane compound (D) may be used alone or in combination of two or more kinds.
• condensates of various silane coupling agents such as condensates of amino group-containing silanes, condensates of amino group-containing silanes and other alkoxysilanes; reactants of amino group-containing silanes and epoxy group-containing silanes, reactants of amino group-containing silanes and (meth)acrylic group-containing silanes, etc. may also be used.
• Dynasylan 6490 and Dynasylan 6498 from Evonik Corporation may be mentioned.
• the amino group-free silane compound (D) is preferably vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, or (methoxymethyl)trimethoxysilane, more preferably vinyltrimethoxysilane or (methoxymethyl)trimethoxysilane, and particularly preferably vinyltrimethoxysilane.
• the amount of the amino group-containing silane compound (C) is not particularly limited and can be set appropriately depending on the desired adhesiveness, but it is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and even more preferably 1 to 8 parts by weight, per 100 parts by weight of the organic polymer (A).
• the curable composition according to the present disclosure can be formulated with a large amount of amino group-containing silane compound (C) while further improving the curability by mixing organic polymer (A) and curing catalyst (B) as described below, and then mixing amino group-containing silane compound (C).
• the amount of amino group-containing silane compound (C) is preferably 2 parts by weight or more, more preferably 3 parts by weight or more, and even more preferably 4 parts by weight or more, per 100 parts by weight of organic polymer (A). It may be 5 parts by weight or more.
• the amount of the non-amino group-containing silane compound (D) is not particularly limited and can be set appropriately depending on the desired physical properties of the silane compound (D), but it is preferably 0 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 1 to 8 parts by weight, per 100 parts by weight of the organic polymer (A).
• the amount of the silane compound (D) may be 3 parts by weight or more, 4 parts by weight or more, or 5 parts by weight or more per 100 parts by weight of the organic polymer (A).
• the total content of the amino group-containing silane compound (C) and the amino group-free silane compound (D) is preferably 5 to 20 parts by weight, more preferably 6 to 15 parts by weight, and even more preferably 7 to 12 parts by weight, per 100 parts by weight of the organic polymer (A).
• the curable composition according to the present disclosure can be produced by mixing an organic polymer (A) and a curing catalyst (B).
• a curing catalyst B
• all of the components constituting the curing catalyst (B) may be added to the organic polymer (A) and mixed all at once, or a portion of the components may be added to the organic polymer (A) and mixed, and then the remaining components may be added to the organic polymer (A).
• the order of mixing the components constituting the curing catalyst (B) is not particularly limited, and the metal compound (b3) may be added to and mixed with the organic polymer (A), and then the carboxylic acid compound (b1) and the cyclic secondary amine compound (b2) having an ester group may be added and mixed. Alternatively, (b1) and (b2) may be added to and mixed with the organic polymer (A), and then (b3) may be added and mixed.
• the order of mixing (b1) and (b2) is not particularly limited, and (b1) may be added and mixed first, followed by (b2), or the reverse order may be used. Also, (b1) and (b2) may be added separately, and then mixed together.
• the curable composition according to the present disclosure contains an amino group-containing silane compound (C) and/or an amino group-free silane compound (D)
• the curable composition can be produced by sequentially or simultaneously mixing the organic polymer (A), the curing catalyst (B), and the amino group-containing silane compound (C) and/or the amino group-free silane compound (D).
• an amino group-containing silane compound (C) it is preferable to mix the organic polymer (A) and the curing catalyst (B) to obtain an intermediate mixture, and then mix the intermediate mixture with the amino group-containing silane compound (C). This makes it easier for the curing catalyst (B) to exert its curing-accelerating effect, and the curability of the resulting curable composition can be improved compared to when the organic polymer (A) and the silane compound (C) are mixed together and then the curing catalyst (B) is mixed.
• a curable composition that exhibits good curability can be produced without reducing the amount of the amino group-containing silane compound (C). It becomes possible to compound a larger amount of the amino group-containing silane compound (C), and a curable composition that combines good curability and adhesiveness can be produced.
• non-amino group-containing silane compound (D) when using a non-amino group-containing silane compound (D), from the viewpoint of further improving the curability, it is preferable to mix the organic polymer (A) with the curing catalyst (B) to obtain an intermediate mixture, and then mix the intermediate mixture with the non-amino group-containing silane compound (D).
• the order of mixing them is not particularly limited.
• the organic polymer (A) or intermediate mixture may be mixed with the amino group-containing silane compound (C) and then the amino group-free silane compound (D) may be added and mixed, or the organic polymer (A) or intermediate mixture may be mixed with the amino group-free silane compound (D) and then the amino group-containing silane compound (C) may be added and mixed.
• the amino group-containing silane compound (C) and the amino group-free silane compound (D) may be added to the organic polymer (A) or intermediate mixture and then mixed together.
• the method for mixing the organic polymer (A) with the curing catalyst (B) and the silane compound (C) and/or (D) is not particularly limited as long as it can achieve uniform mixing, and can be performed using a conventionally known device.
• the temperature during mixing is not particularly limited, and may be room temperature.
• the order in which the other compounding ingredients described below are mixed is not particularly limited. However, it is preferable to add and mix the curing catalyst (B) and the silane compound (C) and/or (D) after mixing the organic polymer (A) with the other compounding ingredients.
• the curable composition according to the present disclosure may contain, as necessary, a plasticizer, a filler, a physical property adjuster, an anti-sagging agent (a thixotropy imparting agent), a stabilizer, and the like.
• the curable composition according to the present disclosure may contain a plasticizer.
• plasticizers 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 (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester (specifically, trade name: Hexamoll DINCH (manufactured by BASF)); dioctyl adipate, sebaceyl phthalate (specifically, trade name: ...
• Such compounds include aliphatic polycarboxylic acid ester compounds such as dioctyl succinate, dibutyl sebacate, diisodecyl succinate, and tributyl acetyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyl ricinoleate; alkylsulfonic acid phenyl esters (specifically, trade name: Mesamoll (manufactured by LANXESS)); phosphate compounds such as tricresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.
• aliphatic polycarboxylic acid ester compounds such as dioctyl succinate, dibutyl sebacate,
• 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 reactive silicon group-containing organic polymer (A). 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.
• the curable composition according to the present disclosure may contain a filler.
• fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, calcined clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, silicic acid anhydride, hydrated silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filaments.
• the above fillers may be used alone or in combination of two or more types.
• the amount of filler used is preferably 1 to 300 parts by weight, and more preferably 10 to 250 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).
• organic balloons or inorganic balloons may be added.
• the balloons are spherical fillers that are hollow inside, and examples of the materials for the balloons include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran.
• the amount of the balloons used is preferably 0.1 to 100 parts by weight, and particularly preferably 1 to 20 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).
• the curable composition according to the present disclosure may contain a physical property adjuster to adjust the tensile properties of the cured product, if necessary.
• the physical property adjuster is not particularly limited, but examples thereof include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishe
• 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 property adjusting agent is preferably used in an amount of 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).
• the curable composition according to the present disclosure may contain an anti-sagging agent, if necessary, to prevent sagging and improve workability.
• the anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and 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 types.
• the anti-sagging agent is preferably used in the range of 0.1 to 20 parts by weight per 100 parts by weight of the reactive silicon group-containing organic polymer (A).
• 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, with hindered phenols being particularly preferred. Examples include Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON), and BHT.
• hindered amine light stabilizers such as TINUVIN 622LD, TINUVIN 144, TINUVIN 292, CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by BASF); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 (all manufactured by ADEKA Corporation); SANOL LS-2626, SANOL LS-1114, SANOL LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and NOCRAC CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used.
• antioxidants such as SONGNOX 4120, Nauguard 445, and OKABEST CLX050 can also be used. Specific examples of 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 reactive silicon group-containing organic polymer (A).
• the curable composition according to the present disclosure may contain a light stabilizer.
• 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. Specific examples of light stabilizers are also described in JP-A-9-194731.
• 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 reactive silicon group-containing organic polymer (A).
• a photocurable substance is blended with the curable composition according to the present disclosure, particularly when an unsaturated acrylic compound is used, it is preferable to use a tertiary amine-containing hindered amine-based light stabilizer as the hindered amine-based light stabilizer in order to improve the storage stability of the composition, as described in JP-A-5-70531.
• tertiary amine-containing hindered amine-based 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 119FL, and CHIMASSORB 944LD (all manufactured by BASF); ADK STAB LA-57, LA-62, LA-63, LA-67, and LA-68 (all manufactured by BASF).
• Examples of light stabilizers include SANOL LS-292, LS-2626, LS-765, LS-744, LS-1114 (all manufactured by Sankyo Lifetech Co., Ltd.), SABOSTAB UV91, SABOSTAB UV119, SONGSORB CS5100, SONGSORB CS622, SONGSORB CS944 (all manufactured by SONGWON), and NOCRAC CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.).
• the curable composition according to the present disclosure may contain an ultraviolet absorber.
• an ultraviolet absorber can improve the surface weather resistance of the cured product.
• ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, triazine-based, substituted acrylonitrile-based, and metal chelate-based compounds, with benzotriazole-based compounds being particularly preferred.
• triazine compounds examples include TINUVIN 400, TINUVIN 405, TINUVIN 477, and TINUVIN 1577ED (all manufactured by BASF); SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON).
• benzophenone compounds examples include SONGSORB 8100 (manufactured by SONGWON).
• the amount of UV absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A). It is preferable to use a phenol or hindered phenol antioxidant in combination with a hindered amine light stabilizer and a benzotriazole UV absorber.
• Addworks IBC760 (manufactured by Clariant) can also be used as a product that contains a mixture of antioxidants, light stabilizers, and UV absorbers.
• the curable composition according to the present disclosure may contain an epoxy resin.
• a composition containing an epoxy resin is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles.
• epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.
• the ratio of organic polymer (A) to epoxy resin is not particularly limited, but it is preferable that the weight ratio of organic polymer (A)/epoxy resin is in the range of 100/1 to 1/100.
• the curable composition according to the present disclosure is preferably used in combination with a curing agent that cures the epoxy resin.
• a curing agent that cures the epoxy resin.
• the epoxy resin curing agent there are no particular limitations on the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used.
• the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.
• the curable composition according to the present disclosure may contain various additives as necessary for the purpose of adjusting the various physical properties of the curable composition or the cured product.
• additives include silicates, surface improvers, flame retardants, foaming agents, curability regulators, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.
• the curable composition according to the present disclosure can be prepared as a one-component curable composition in which all ingredients are mixed in advance, sealed, and stored, and then cured by moisture in the air after application. It is also possible to prepare a two-component curable composition in which a curing agent containing ingredients such as a curing catalyst, filler, plasticizer, and water is prepared separately from a base agent containing a reactive silicon group-containing organic polymer (A), and the base agent and curing agent are mixed together before use.
• a curing agent containing ingredients such as a curing catalyst, filler, plasticizer, and water
• the curable composition When the curable composition is of one component type, all the ingredients are mixed in advance, so it is preferable to dehydrate the ingredients containing water before use, or to dehydrate them by reducing pressure during mixing.
• the curable composition When the curable composition is of two component type, there is no need to mix a curing catalyst into the base agent containing the reactive silicon group-containing organic polymer (A), so even if the ingredients contain a small amount of water, there is little risk of gelation, but it is preferable to dehydrate them when long-term storage stability is required.
• a dehydration method a heat drying method is suitable for solid substances such as powders, and a reduced pressure dehydration method or a dehydration method using synthetic zeolite, activated alumina, silica gel, etc. is suitable for liquid substances.
• an isocyanate compound may be mixed to react the isocyanate group with water to dehydrate it.
• storage stability can be further improved by adding lower alcohols such as methanol and ethanol; or alkoxysilane compounds such as methyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, phenyltrimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane.
• partially condensed silane compounds such as Evonik's Dynasylan 6490 can also 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 reactive silicon group-containing organic polymer (A).
• the curable composition according to the present disclosure can be used as a construction sealant, industrial adhesive, waterproof coating, adhesive raw material, etc. It can also be used as a sealant for buildings, ships, automobiles, roads, etc. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer, it can also be used as various types of sealing compositions and adhesive compositions. In addition to being used as a normal adhesive, it can also be used as a contact adhesive. It is also useful as a food packaging material, cast rubber material, molding material, and paint.
• a curable composition comprising an organic polymer (A) having a reactive silicon group represented by the formula: the curing catalyst (B) comprises a carboxylic acid compound (b1), a cyclic secondary amine compound (b2) having an ester group, and a metal compound (b3);
• the metal compound (b3) is represented by the following general formula (2): M (OR 2 ) d Y ed (2) (In the formula, M represents a metal atom having a valence e selected from the group consisting of titanium metal, aluminum metal, zirconium metal, and hafnium metal. e represents the valence of the central metal.
• R2 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
• Y represents a chelate coordination compound.
• d represents 0 or an integer from 1 to e.
• the curable composition is a compound represented by the formula: [Item 2] 2.
• [Item 3] 3 3.
• the curable composition according to item 2 wherein the main chain structure of the organic polymer (A) contains a polyoxyalkylene-based polymer and a (meth)acrylic acid ester-based polymer.
• [Item 12] 10 10.
• a method for producing the curable composition according to claim 10, comprising the steps of: a step of mixing the organic polymer (A) and the curing catalyst (B) to obtain an intermediate mixture, and then mixing the intermediate mixture with the silane compound (C) and the silane compound (D).
• the number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.
• Liquid delivery system Tosoh HLC-8120GPC Column: Tosoh TSKgel Super H series Solvent: THF Molecular weight: polystyrene equivalent Measurement temperature: 40°C
• the average number of silyl groups per terminal or per molecule of the polymer shown in the examples was calculated by H-NMR (measured in CDCl 3 solvent using AVANCE III HD-500 manufactured by Bruker).
• hexane solution was further mixed and stirred with 300 parts by weight of water, and the water was removed again by centrifugation, and the hexane was removed by volatilization under reduced pressure.
• a bifunctional polypropylene oxide having an allyl group at the end and a number average molecular weight of about 28,500 was obtained.
• trimethoxysilyl-terminated polyoxypropylene (A-1) 100 parts by weight of the resulting allyl-terminated polypropylene oxide were reacted with 0.8 molar equivalent of trimethoxysilane relative to the allyl group of the allyl-terminated polypropylene oxide at 90°C for 5 hours using 150 ppm of a 2-propanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% as a catalyst, to obtain trimethoxysilyl-terminated polyoxypropylene (A-1).
• the number of trimethoxysilyl groups was about 0.8 per polymer chain end.
• trimethoxysilyl-terminated polyoxypropylene (A-2) The number of trimethoxysilyl groups per polymer chain end was about 0.9.
• allyl polymer Using 150 ppm of a platinum vinylsiloxane complex with a platinum content of 3 wt % in isopropanol as a catalyst for 100 parts by weight of polymer, 0.7 molar equivalents of methyldimethoxysilane relative to the allyl group of allyl-terminated polypropylene oxide were reacted at 90° C. for 5 hours. This resulted in the production of methyldimethoxysilyl-terminated polypropylene oxide (A-3). The number of methyldimethoxysilyl groups per polymer chain end was about 0.7.
• Allyl chloride was added to convert the terminal hydroxyl groups to allyl groups, thereby obtaining an allyl polymer having a number average molecular weight of about 28,500 and having a plurality of terminal allyl groups.
• the allyl polymer was purified in the same manner as in Synthesis Example 1. Using 150 ppm of an isopropanol solution of a platinum vinylsiloxane complex having a platinum content of 3 wt % as a catalyst, the allyl group of the allyl-terminated polypropylene oxide was reacted with the allyl group to obtain 100 parts by weight of the allyl polymer. The resulting mixture was reacted with 0.8 molar equivalents of trimethoxysilane at 90° C. for 5 hours to obtain trimethoxysilyl-terminated polypropylene oxide (A-4). The number of trimethoxysilyl groups per polymer chain end was about 1.5. There were 100 pieces.
• Example 1 To 100 parts by weight of the organic polymer (A-1) having a reactive silicon group, colloidal calcium carbonate (Shiraishi Calcium Co., Ltd., product name: Hakuenka CCR), heavy calcium carbonate (Shiraishi Calcium Co., Ltd., product name: Whiten SB), plasticizer (BASF Corporation, product name: Hexamoll DINCH), pigment (Ishihara Sangyo Kaisha, Ltd., product name: Typen R820), thixotropic agent (ARKEMA Corporation, product name: Crayvallac SLT), antioxidant (BASF Corporation, product name: Irganox 1010), ultraviolet absorber (BASF Corporation, product name: Tinuvin 326), and light stabilizer (BASF Corporation, product name: Tinuvin 770) were added in the amounts (parts by weight) shown in Table 1, respectively, and mixed using a spatula, and then the mixture was passed through a three-roll mill three times to be dispersed.
• colloidal calcium carbonate Shiraishi Calcium Co.,
• the mixture was dehydrated under reduced pressure using a planetary mixer, and the mixture was filled into a moisture-proof cartridge to form a base material.
• the base material was extruded from the cartridge under an atmosphere of 23°C and 50% relative humidity, and weighed into a plastic container.
• Dynasylan VTMO was added to the base material as an amino group-free silane compound (D) in the amount (parts by weight) shown in Table 1 and mixed, and then Dynasylan AMMO was added as an amino group-containing silane compound (C) and mixed.
• Al(O s Bu) 3 was added as a metal compound (b3) and mixed.
• ethyl 4-piperidine carboxylate was added as a cyclic secondary amine compound (b2) having an ester group and mixed.
• neodecanoic acid was added as a carboxylic acid (b1) and mixed to obtain a curable composition.
• the curable composition was filled into a mold about 5 mm thick with a spatula under an atmosphere of 23°C and 50% relative humidity, and the time when the surface was smoothed to a flat surface was defined as the curing start time.
• the surface was touched with the spatula, and the time when the composition no longer adhered to the spatula was defined as the skinning time, and the curing time (curability) was measured.
• the measurement results are shown in Table 1.
• Example 2 A curable composition was obtained in the same manner as in Example 1, except that Ti( OiPr ) 4 was used as the metal compound (b3) instead of Al( OsBu ) 3 , and the curing time (curability) was measured. The measurement results are shown in Table 1.
• Example 1 A curable composition was obtained in the same manner as in Example 1 or 2, except that the cyclic secondary amine compound (b2) having an ester group was not used, and 0.8 parts by weight of 3,5-dimethylpiperidine, a cyclic secondary amine compound having no ester group, was used instead, and the curing time (curability) was measured. The measurement results are shown in Table 1.
• Metal compound (b3) Al(O s Bu) 3 trisec-butoxyaluminum, manufactured by Tokyo Chemical Industry Co., Ltd.
• Ti(O i Pr) 4 titanium tetraisopropoxide, manufactured by Tokyo Chemical Industry Co., Ltd.
• Cyclic secondary amine compound not having an ester group 3,5-Dimethylpiperidine: manufactured by Tokyo Chemical Industry Co., Ltd.
• Neodecanoic acid Made by Hexion
• Example 3 A curable composition was obtained in the same manner as in Example 1 or 2, except that the organic polymer (A-2) was used instead of the organic polymer (A-1), and the curing time (curability) was measured. The measurement results are shown in Table 2.
• Examples 5 to 16 Under an atmosphere of 23°C and relative humidity of 50%, the amount (parts by weight) of the amino group-free silane compound (D) was added and mixed with 100 parts by weight of the organic polymer (A-1) or (A-3) having a reactive silicon group, respectively, in the amounts (parts by weight) shown in Table 3, and then the amino group-containing silane compound (C) was added and mixed. Then, the metal compound (b3) was added and mixed. Then, the cyclic secondary amine compound (b2) having an ester group was added and mixed. Finally, the carboxylic acid (b1) was added and mixed to obtain a curable composition. The curing time (curability) was measured in the same manner as in Example 1.
• Cyclic secondary amine compound having an ester group (b2) Methyl 4-piperidinecarboxylate: manufactured by Tokyo Chemical Industry Co., Ltd. Ethyl 3-piperidinecarboxylate: manufactured by Tokyo Chemical Industry Co., Ltd.
• Tyzor 9000 titanium tetra-tert-butoxide, manufactured by Dorf Ketal TC-750: titanium diisopropoxybis(ethyl acetoacetate), manufactured by Matsumoto Fine Chemical Co., Ltd.
• Tyzor KE-6 titanium diisobutoxybis(ethyl acetoacetate), manufactured by Dorf Ketal
• Example 17 to 27 The order of adding and mixing the amino group-free silane compound (D), amino group-containing silane compound (C), metal compound (b3), cyclic secondary amine compound (b2) having an ester group, and carboxylic acid (b1) to the base resin obtained in Example 1 was changed, and the curable composition was obtained in the same manner as in Example 1, except that the type of metal compound (b3) was changed, and the curing time (curability) was measured.
• the measurement results are shown in Table 4. The details of the mixing order are described below for each example.
• Example 17 Method 1 First, the metal compound (b3) was added to the base material and mixed. Then, the carboxylic acid (b1) was added and mixed. Then, the cyclic secondary amine compound (b2) having an ester group was added and mixed. Then, the amino group-free silane compound (D) was added and mixed. Finally, the amino group-containing silane compound (C) was added and mixed to obtain a curable composition.
• Example 18, Method 2 First, the metal compound (b3) was added to the base material and mixed. Then, the cyclic secondary amine compound (b2) having an ester group was added and mixed. Then, the carboxylic acid (b1) was added and mixed. Then, the amino group-free silane compound (D) was added and mixed. Finally, the amino group-containing silane compound (C) was added and mixed to obtain a curable composition.
• Example 19 First, the metal compound (b3) was added to the main component and mixed. Then, the cyclic secondary amine compound (b2) having an ester group and the carboxylic acid (b1) were added and mixed. Then, the amino group-free silane compound (D) was added and mixed. Finally, the amino group-containing silane compound (C) was added and mixed to obtain a curable composition.
• Example 20, Method 4 First, the metal compound (b3) was added to the main component and mixed. Then, the cyclic secondary amine compound (b2) having an ester group and the carboxylic acid (b1) were added and mixed. Then, the amino group-free silane compound (D) and the amino group-containing silane compound (C) were added and mixed to obtain a curable composition.
• Example 21, Method 5 First, the cyclic secondary amine compound (b2) having an ester group and the carboxylic acid (b1) were added to the main component and mixed, and then the metal compound (b3) was added and mixed. Next, the amino group-free silane compound (D) and the amino group-containing silane compound (C) were added and mixed to obtain a curable composition.
• Example 22 Method 6 First, the amino group-free silane compound (D) and the amino group-containing silane compound (C) were added to the base material and mixed. Then, the metal compound (b3) was added and mixed. Finally, the cyclic secondary amine compound (b2) having an ester group and the carboxylic acid (b1) were added and mixed to obtain a curable composition.
• Example 23 Method 7 First, the amino group-free silane compound (D) was added to the base material and mixed, and then the amino group-containing silane compound (C) was added and mixed. Next, the metal compound (b3) was added and mixed. Then, the cyclic secondary amine compound (b2) having an ester group was added and mixed. Finally, the carboxylic acid (b1) was added and mixed to obtain a curable composition.
• the mixing order of Method 7 in Example 23 was the same as that in Examples 1 to 16 and Comparative Example 1.
• Example 24, Method 8 First, the metal compound (b3) was added to the base material and mixed, and then the amino group-free silane compound (D) was added and mixed. Then, the amino group-containing silane compound (C) was added and mixed. Then, the cyclic secondary amine compound (b2) having an ester group was added and mixed. Finally, the carboxylic acid (b1) was added and mixed to obtain a curable composition.
• Example 25 (Example 25, Method 9) First, the metal compound (b3) was added to the base material and mixed, and then the amino group-containing silane compound (C) was added and mixed. Then, the amino group-free silane compound (D) was added and mixed. Then, the cyclic secondary amine compound (b2) having an ester group was added and mixed. Finally, the carboxylic acid (b1) was added and mixed to obtain a curable composition.
• Example 26 An amino group-containing silane compound (C), an amino group-free silane compound (D), a cyclic secondary amine compound having an ester group (b2), and a carboxylic acid (b1) were added to the main component and mixed, and then a metal compound (b3) was added and mixed to obtain a curable composition.
• Example 2 A curable composition was obtained in the same manner as in Example 23 (Method 7), except that the cyclic secondary amine compound (b2) having an ester group was not used, and instead, 3,5-dimethylpiperidine, a cyclic secondary amine compound having no ester group, was used, and the curing time (curability) of the curable composition was measured. The measurement results are shown in Table 4.
• Example 28 to 32 Except for changing the type of the cyclic secondary amine compound (b2) having an ester group or the metal compound (b3), a curable composition was obtained in the same manner as in Example 19 (Method 3), and the curing time (curability) was measured. The measurement results are shown in Table 5.
• Metal compound (b3) Ti(OBu) 4 titanium tetrabutoxide, manufactured by Tokyo Chemical Industry Co., Ltd.
• Neodecanoic acid (carboxylic acid (b1)), ethyl 4-piperidinecarboxylate (cyclic secondary amine compound (b2) having an ester group), and Tyzor KE-6 (metal compound (b3)) were mixed in a weight ratio of 4:0.8:1 to obtain a catalyst mixture.
• the amino group-free silane compound (D) was added to each of the base materials shown in Table 6 and mixed, and then the amino group-containing silane compound (C) was added and mixed.
• 4 parts by weight of the obtained catalyst mixture was added and mixed to obtain a curable composition, and the curing time (curability) was measured.
• the measurement results are shown in Table 6.
• a metal compound (b3) was added to 70 parts by weight of an organic polymer (A-3) having a reactive silicon group and mixed. Then, a cyclic secondary amine compound (b2) having an ester group and a carboxylic acid (b1) were added and mixed. Then, an amino group-free silane compound (D) and an amino group-containing silane compound (C) were added and mixed. Finally, 4 parts by weight of Ancamine K54 (2,4,6-tris(dimethylaminomethyl)phenol, manufactured by Evonik) were added as an epoxy resin curing agent and mixed to obtain an agent A.
• Ancamine K54 2,4,6-tris(dimethylaminomethyl)phenol, manufactured by Evonik
• Agent B was obtained by mixing 30 parts by weight of jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) as an epoxy resin and 0.5 parts by weight of water. The A and B components were thoroughly mixed and the curing time (curability) was measured by the method described above. The results are shown in Table 7.
• Example 38 A metal compound (b3) was added to 100 parts by weight of an organic polymer (A-3) having a reactive silicon group and mixed. Then, a cyclic secondary amine compound (b2) having an ester group and a carboxylic acid (b1) were added and mixed. Then, an amino group-free silane compound (D) and an amino group-containing silane compound (C) were added and mixed to obtain an A agent.
• Agent B was obtained by mixing 30 parts by weight of Acclaim 12200 (a polyether polyol plasticizer, manufactured by Covestro) as a plasticizer and 0.5 parts by weight of water. The curing time (curability) was measured in the same manner as in Example 37. The results are shown in Table 7.

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