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
  • 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
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0091—Complexes with metal-heteroatom-bonds
• • 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
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides

Definitions

• the present invention relates to a curable composition that contains an organic polymer having a reactive silicon group, a curing catalyst containing a specific compound, and a silane condensate.
• Organic polymers that have at least one reactive silicon group in the molecule can be crosslinked by forming siloxane bonds accompanied by hydrolysis of the silyl group due to moisture, even at room temperature. It is known that organic polymers that have reactive silicon groups have the property of giving a rubber-like cured product through such a crosslinking reaction.
• curable compositions such as sealants, adhesives, paints, and waterproofing materials
• the curable compositions are required to have a variety of properties, including curability, adhesion, workability, mechanical properties of the cured product, and waterproofing.
• Curable compositions containing organic polymers with reactive silicon groups are usually cured using a silanol condensation catalyst, such as an organotin compound with a carbon-tin bond, such as dibutyltin bis(acetylacetonate). Silanol condensation catalysts are also called curing catalysts.
• a silanol condensation catalyst such as an organotin compound with a carbon-tin bond, such as dibutyltin bis(acetylacetonate).
• Silanol condensation catalysts are also called curing catalysts.
• the toxicity of organotin compounds has come to light, and the use of non-tin catalysts has been proposed (Patent Document 1).
• curable compositions containing organic polymers having reactive silicon groups bifunctional dialkoxysilyl groups such as dimethoxymethylsilyl groups are sometimes used as the reactive silicon groups in order to obtain cured products that are highly elongated and flexible.
• various silane compounds typified by silane coupling agents, may be blended into a curable composition containing an organic polymer having a reactive silicon group for the purposes of improving the stability of the curable composition or imparting adhesion to an adherend.
• Patent Document 1 proposes the use of a combination of DBU and diisopropoxytitanium bis(ethylacetoacetate) as a non-tin curing catalyst in a curable composition containing a trimethoxysilane coupling agent and an organic polymer having a dimethoxymethylsilyl group.
• the curing speed of the curable composition described in Patent Document 1 was not sufficient. Therefore, there is a demand for an improvement in the curing speed of a curable composition containing an organic polymer having a difunctional dialkoxysilyl group, a silane compound, and a non-tin curing catalyst.
• the present invention has been made in consideration of the above problems, and aims to provide a curable composition that contains an organic polymer having a bifunctional dialkoxysilyl group as a reactive silicon group, a silane compound, and a non-tin curing catalyst, and exhibits rapid curing properties.
• the inventors discovered that the above problems could be solved by using a combination of an amidine compound and a titanium compound as the curing catalyst and a silane condensate of a specific structure as the silane compound in a curable composition containing an organic polymer having a bifunctional dialkoxysilyl group as the reactive silicon group, a silane compound, and a non-tin curing catalyst, and thus completed the present invention.
• a curable composition comprising an organic polymer (A), a curing catalyst (B), and a silane condensate (C),
• the organic polymer (A) is represented by the following formula (1): -SiR 1 X 2 (1)
• R 1 is a hydrocarbon group having 1 to 20 carbon atoms
• X is a hydroxyl group or a hydrolyzable group, and the two Xs may be the same or different.
• the curing catalyst (B) contains an amidine compound (b1) and a titanium compound (b2)
• the amidine compound (b1) is represented by the following formula (2):
• R 2 N CR 3 -NR 4 2 (2)
• R 4 are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent, and two R 4s may be the same or different, and any two of R 2 , R 3 , and the two R 4s may
• the present invention provides a curable composition that contains an organic polymer having a bifunctional dialkoxysilyl group as a reactive silicon group, a silane compound, and a non-tin curing catalyst, and exhibits rapid curing properties.
• the curable composition contains an organic polymer (A), a curing catalyst (B), and a silane condensate (C).
• the organic polymer (A) has a reactive silicon group represented by the following formula (1). -SiR 1 X 2 (1)
• R1 is a hydrocarbon group having 1 to 20 carbon atoms.
• X is a hydroxyl group or a hydrolyzable group. The two X's may be the same or different.
• the curing catalyst (B) contains an amidine compound (b1) and a titanium compound (b2).
• the amidine compound (b1) is a compound represented by the following formula (2).
• R 2 N CR 3 -NR 4 2 (2)
• R 2 , R 3 , and R 4 are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent.
• the two R 4s may be the same or different. Any two of R 2 , R 3 , and the two R 4s may be bonded to form a ring.
• the titanium compound (b2) is a compound represented by the following formula (3) or a condensate thereof.
• R5 is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
• Y is a chelate coordination compound.
• d is an integer of 0 to 4.
• the silane condensate (C) is a compound represented by the following formula (4).
• R 6 is a methyl group or an ethyl group, and R 6 may be the same or different.
• R 7 and R 8 are hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent, and R 7 and R 8 may be the same or different.
• e and f are integers of 1 to 50.
• the curable composition may also contain various other additives as needed.
• curable composition may contain.
• Organic polymer (A) has a reactive silicon group represented by the above formula (1).
• the organic polymer (A) has a polymer backbone and a polymer chain end bonded to the polymer backbone.
• the polymer backbone is also referred to as the "main chain structure.”
• the polymer backbone is a structure in which multiple structural units derived from monomers are bonded in succession.
• the monomer may be of one type or of multiple types.
• polymer chain end refers to a portion located at the end of the organic polymer (A).
• the number of polymer chain ends of the organic polymer (A) is 2 when the main chain structure is linear, and is 3 or more when the polymer backbone is branched.
• the organic polymer (A) is a mixture of a polymer having a linear main chain structure and a polymer having a branched main chain structure, the number of polymer chain ends is an average value between 2 and 3.
• the reactive silicon group may be present in the polymer backbone and at the polymer chain end. Two or more reactive silicon groups may be present at the polymer chain end.
• the curable composition is used as an adhesive, a sealant, an elastic coating agent, a pressure sensitive adhesive, etc., it is preferable that the reactive silicon group in the organic polymer (A) is present at the polymer chain end.
• the reactive silicon group is a group that can generate a silanol group by hydrolysis.
• the organic polymer (A) is crosslinked by a condensation reaction between the silanol groups.
• the reactive silicon group is a group represented by the following formula (1). -SiR 1 X 2 (1)
• R1 is a hydrocarbon group having 1 to 20 carbon atoms.
• X is a hydroxyl group or a hydrolyzable group, and the two X's may be the same or different.
• R 1 in formula (1) examples include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, a 2-ethylhexyl group, and an n-dodecyl group; unsaturated hydrocarbon groups such as a vinyl group, an isopropenyl group, and an allyl group; cycloalkyl groups such as a cyclohexyl group; aryl groups such as a phenyl group, a toluyl group, and a 1-naphthyl group; aralkyl groups such as a benzyl group, etc.
• alkyl groups and aryl groups are preferred, with methyl groups, ethyl groups, and phenyl groups being more preferred, methyl groups and ethyl groups being
• X in formula (1) is a hydroxyl group or a hydrolyzable group.
• the hydrolyzable group is not particularly limited and may be a known hydrolyzable group. Specific examples of hydrolyzable groups include hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, alkoxy groups, acyloxy groups, ketoximate groups, and alkenyloxy groups are preferred, and alkoxy groups such as methoxy groups and ethoxy groups are more preferred because they are mildly hydrolyzable and easy to handle.
• the two Xs in formula (1) may be the same group or different groups.
• the reactive silicon group represented by formula (1) is not particularly limited. Specific examples of the reactive silicon group represented by formula (1) include a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a dimethoxyphenylsilyl group. Among these, the dimethoxymethylsilyl group is preferred because the raw material is easily available.
• the main chain structure of the organic polymer (A) is not particularly limited, and may be any of various known main chain structures.
• Specific examples of the main chain structure include polyoxyalkylene polymers such as polyoxyethylene polymers, polyoxypropylene polymers, polyoxybutylene polymers, polyoxytetramethylene polymers, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, isobutylene-isoprene copolymers, polybutadiene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polycondensates of dibasic acids such as adipic acid and glycols; and ring-opening polymers of lactones; (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester mono
• Polyoxyalkylene polymers and (meth)acrylic acid ester polymers are particularly preferred as the main chain structure, since they have excellent deep curing properties as a one-component composition due to their high moisture permeability, and also have excellent adhesion.
• main chain structure polyoxyalkylene polymers are more preferred, and polyoxypropylene is even more preferred.
• the polyoxyalkylene polymer is a polymer having a repeating unit represented by -R 9 -O-.
• R 9 is a linear or branched alkylene group having 1 to 14 carbon atoms.
• R 9 is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.
• Specific examples of the repeating unit represented by -R 9 -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 repeating units in an amount of 50% by weight or more, preferably 80% by weight or more, of the polymer main chain structure is preferred as the polyoxyalkylene-based polymer, because such a polyoxyalkylene-based polymer is amorphous and has a relatively low viscosity.
• the main chain structure of the polyoxyalkylene polymer may be linear or branched.
• a polyoxyalkylene polymer a polymer obtained by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator is preferred.
• cyclic ether compound examples include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, tetrahydrofuran, etc. These cyclic ether compounds may be used alone or in combination of two or more. Among these cyclic ether compounds, propylene oxide is particularly preferred since it is possible to obtain an amorphous polyether polymer having 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 polyoxyalkylene polymers 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 glycol, glycerin, trimethylolmethane, trimethylolprop
• the method for synthesizing the polyoxyalkylene polymer is not particularly limited.
• methods for synthesizing polyoxyalkylene polymers include a polymerization method using an alkali catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound with porphyrin as disclosed in JP-A-61-215623, a polymerization method using a composite metal cyanide complex catalyst as disclosed in JP-B-46-27250, JP-B-59-15336, U.S. Pat. Nos.
• the main chain structure of the organic polymer (A) may be a polyoxyalkylene polymer containing bonds other than ether bonds, such as urethane bonds and urea bonds, to the extent that the desired effect is not significantly impaired.
• Specific examples of polymers having such a main chain structure include polyurethane prepolymers and polyurea prepolymers.
• the polyurethane prepolymer can be obtained by a known method such as a method of reacting a polyol compound with a polyisocyanate compound, and the polyurea prepolymer can be obtained by a known method such as a method of reacting a polyamine compound with a polyisocyanate compound.
• the main chain structure may be a prepolymer having a combination of a urethane bond and a urea bond, which is obtained by reacting a polyol compound and a polyamine compound with a polyisocyanate compound.
• polyol compounds include polyether polyols, polyester polyols, polycarbonate polyols, and polyether polyester polyols.
• polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, and hexamethylene diisocyanate.
• the ends of the polyurethane prepolymer may be either hydroxyl groups or isocyanate groups.
• the ends of the polyurea prepolymer may be either amino groups or isocyanate groups.
• the strength of the cured product may decrease due to cleavage of the urethane bonds, urea bonds, or ester bonds in the main chain structure caused by heat, etc.
• the curability of the curable composition may be improved.
• R 10 is a hydrogen atom or an organic group which may have a substituent.
• the number of amide bonds is preferably 1 to 10, more preferably 1.5 to 5, and even more preferably 2 to 3, on average per molecule.
• the curable composition has good curability, the viscosity of the organic polymer (A) is low, and the organic polymer (A) and the curable composition are easy to handle.
• 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 is most preferable.
• the organic polymer (A) is preferably a polymer obtained by introducing a reactive silicon group into a polymer by any one of the following methods (a) to (d).
• R 1 and X are the same as those in formula (1).
• (d) A method in which a hydroxyl-terminated organic polymer is reacted with a polyisocyanate compound to synthesize an NCO-terminated organic polymer, and then the terminal NCO group is reacted with a silane compound represented by HNR 11 -W-SiR 1 X 2 or HS-W-SiR 1 X 2.
• W is a divalent organic group.
• R 11 is a hydrogen atom or an alkyl group.
• R 1 and X are the same as those in formula (1).
• 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 polymer (A) obtained by using a silane compound in which W is methylene exhibits very high curability.
• Method (a) is preferred because it is easy to obtain an organic polymer (A) that has good storage stability.
• Methods (b), (c), and (d) are preferred because they can achieve a high conversion rate in a relatively short reaction time.
• Examples of such methods include the method proposed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, and JP-A-61-218632, which introduces reactive silicon groups by hydrosilylation or the like into a polyoxypropylene polymer having 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 the method proposed in JP-A-3-72527.
• the number average molecular weight of the organic polymer (A) is not particularly limited.
• the number average molecular weight of the organic polymer (A) is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000, as a polystyrene-equivalent molecular weight in GPC.
• the number average molecular weight is within the above range, the amount of reactive silicon groups introduced is appropriate, making it easy to obtain an organic polymer (A) that has a manageable viscosity and excellent workability while keeping production costs within an appropriate range.
• the polymer precursor before the introduction of reactive silicon groups can be subjected to 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 to directly measure the end group concentration, and the molecular weight of the organic polymer (A) can be shown as the end group converted molecular weight calculated taking into account the polymer structure (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 molecular weight distribution (Mw/Mn) of the organic polymer (A) is not particularly limited. It is preferable that the molecular weight distribution of the organic polymer (A) is narrow. Specifically, the molecular weight distribution is preferably 1.6 or less, more preferably 1.4 or less, even more preferably 1.3 or less, and particularly preferably 1.2 or less.
• the molecular weight distribution of the organic polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
• the reactive silicon groups of the organic polymer (A) are present at the polymer chain end.
• the number of reactive silicon groups per polymer chain end 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 reactive silicon groups is 0.5 or more, the curability of the organic polymer (A) and the curable composition is good, and the cured product of the curable composition has good rubber elasticity.
• the average number of reactive silicon groups in one molecule is preferably 1 to 7, more preferably 1 to 4, and particularly preferably 1 to 3.
• an organic polymer having two or more reactive silicon groups at the polymer chain end can be used as the organic polymer (A).
• Such an organic polymer (A) exhibits high curability, and the resulting cured product is expected to have high strength and high recovery.
• organic polymers (A) include various reactive silicon group-containing polyoxypropylene products such as Kaneka MS Polymer (registered trademark) and Kaneka Silyl (registered trademark), reactive silicon group-containing poly(meth)acrylic ester products such as Kaneka TA Polymer (registered trademark) and KANEKA XMAP (registered trademark), and reactive silicon group-containing polyisobutylene products such as EPION (registered trademark). All of these commercially available organic polymers (A) are products of Kaneka Corporation.
• Kaneka MS Polymer registered trademark
• Kaneka Silyl registered trademark
• reactive silicon group-containing poly(meth)acrylic ester products such as Kaneka TA Polymer (registered trademark) and KANEKA XMAP (registered trademark)
• reactive silicon group-containing polyisobutylene products such as EPION (registered trademark). All of these commercially available organic polymers (A) are products of Kaneka Corporation.
• the curable composition contains a curing catalyst (B) that cures the organic polymer (A) by hydrolysis and condensation.
• the curing catalyst (B) contains an amidine compound (b1) and a titanium compound (b2).
• amidine compound (b1) The amidine compound (b1) is a compound represented by the following formula (2).
• R 2 N CR 3 -NR 4 2 (2)
• R 2 , R 3 , and R 4 are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent.
• the two R 4s may be the same or different. Any two of R 2 , R 3 , and the two R 4s may be bonded to form a ring.
• optionally substituted hydrocarbon groups are bonded to form a ring, one hydrogen atom is removed from each of the two optionally substituted hydrocarbon groups, and the atoms to which the removed hydrogen atoms were bonded on the optionally substituted hydrocarbon groups are linked by a single bond to form the ring.
• the hydrogen atom of R3 and one hydrogen atom on the hydrocarbon group which may have a substituent are removed, and the carbon atom to which the hydrogen atom of R3 was bonded and the atom to which the removed hydrogen atom on the hydrocarbon group which may have a substituent of R4 was bonded are linked by a single bond to form a ring.
• R 2 , R 3 , and two R 4 are bonded to form a ring, for example, R 2 and one R 4 may be bonded to form a ring, and R 3 and the other R 4 may be bonded to form a ring, or R 2 and R 3 may form a ring, and two R 4s may form a ring.
• the hydrocarbon groups represented by R 2 , R 3 , and R 4 may have a substituent.
• substituents that the hydrocarbon groups represented by R 2 , R 3 , and R 4 may have include a halogen atom, an amino group, an alkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group.
• the number of carbon atoms of the hydrocarbon groups represented by R 2 , R 3 , and R 4 excluding the number of carbon atoms of the substituents is preferably 1-12, more preferably 1-6, and even more preferably 1-4.
• hydrocarbon group as R 2 , R 3 , and R 4 are the same as the specific examples of the hydrocarbon group as R 1.
• Groups exemplified as the hydrocarbon group as R 1 that are substituted with the above-mentioned substituents are also preferred.
• the ring formed by combining R 2 , R 3 and two of the two R 4s may be a five-membered ring, a six-membered ring or a seven-membered ring, preferably a six-membered ring or a seven-membered ring.
• amidine compound (b1) an amidine containing at least one ring structure (ie, a cyclic amidine) is preferred, and a cyclic amidine containing two ring structures (ie, a bicyclic amidine) is more preferred.
• amidine compounds include cyclic amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine, and 1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine; bicyclic amidines such as DBU (1,8-diazabicyclo[5.4.0]-7-undecene) and DBN (1,5-diazabicyclo[4.3.0]-5-nonene); guanidine, di Cyandiamide, 1-methylguanidine, 1-
• the amount of amidine compound (b1) used is preferably 0.1 to 4.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, and even more preferably 0.3 to 2.0 parts by weight, per 100 parts by weight of organic polymer (A).
• titanium compound (b2) The titanium compound (b2) is a compound represented by the following formula (3). Ti(OR 5 ) d Y 4-d (3)
• R5 is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
• Y is a chelate coordination compound.
• d is an integer of 0 to 4.
• the hydrocarbon group represented by R5 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• the hydrocarbon group represented by R5 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may have one or more unsaturated bonds.
• the structure of the aliphatic hydrocarbon group may be linear, branched, or cyclic, or may be a combination of these structures.
• the hydrocarbon group represented by R5 may have a substituent.
• the hydrocarbon group represented by R5 does not have a substituent.
• substituent that the hydrocarbon group represented by R5 may have are the same as the examples of the substituent that the hydrocarbon groups represented by R2 , R3 , and R4 may have.
• the hydrocarbon group represented by R 5 preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, and further preferably has 1 to 4 carbon atoms.
• the hydrocarbon group represented by R5 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group.
• the chelating coordination compound represented by Y is preferably a bidentate organic ligand.
• the chelating coordination compound include ⁇ -diketones and ⁇ -ketoesters.
• Specific examples of ⁇ -diketones include acetylacetone (ACAC), trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, thenoyltrifluoroacetone, dipivaloylmethane, dibenzoylmethane, and ascorbic acid.
• ⁇ -ketoesters include methyl acetoacetate, ethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, n-propyl acetoacetate, iso-propyl acetoacetate, n-butyl acetoacetate, iso-butyl acetoacetate, tert-butyl acetoacetate, 2-methoxyethyl acetoacetate, and methyl 3-oxopentanoate.
• titanium compound (b2) examples include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium, ethoxytriisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxydibut,
• titanium compound (b2) a single component may be used, or multiple components may be used in combination.
• the titanium compound (b2) may be used alone or in combination of two or more components.
• the titanium compound (b2) and the amidine compound (b1) may be added separately to the curable composition, or may be mixed together in advance and then added to the curable composition as a mixture.
• the amount of the titanium compound (b2) used is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 4.5 parts by weight, and even more preferably 1.0 to 4.0 parts by weight, based on 100 parts by weight of the organic polymer (A).
• the weight ratio (b2)/(b1) of the titanium compound (b2) to the amidine compound (b1) is preferably from 1.0 to 10, more preferably from 1.0 to 5.0.
• silane condensate (C) is a compound having a structure represented by the following formula (4).
• R 6 is a methyl group or an ethyl group.
• R 6 may be the same or different.
• R 7 and R 8 are hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent.
• R 7 and R 8 may be the same or different.
• e and f are integers from 1 to 50.
• the silane condensate (C) can be obtained by condensing a silane compound monomer having a hydrolyzable silicon group, followed by oligomerization or polymerization.
• Specific examples of the silane compound monomer that forms the silane condensate (C) include vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; allyltrialkoxysilanes such as allyltrimethoxysilane and allyltriethoxysilane; ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriethoxysilane, ⁇ -(2-(2-aminoethyl)aminopropyltriethoxysilane, ⁇
• alkyltrialkoxysilanes such as cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cycloheptyltrimethoxysilane, cycloheptyltriethoxysilane, 2-methylcyclohexyltrimethoxysilane, 2-methylcyclohexyltriethoxysilane, 3-methylcyclohexyltriethoxysilane, 4-methylcyclohexyltriethoxysilane, 5-methylcyclo
• silane condensate (C) it is preferable to form the silane condensate (C) using at least one trialkoxysilane selected from vinyltrialkoxysilane, amino group-containing trialkoxysilane, and alkyltrialkoxysilane, and it is more preferable to form the silane condensate (C) using at least one trimethoxysilane selected from vinyltrimethoxysilane, amino group-containing trimethoxysilane, and alkyltrimethoxysilane.
• silane condensates include Dynasylan 6490, Dynasylan 6498, and Dynasylan 1146 manufactured by Evonik.
• the curable composition cures faster than when a silane compound monomer is added to the curable composition.
• the amount of the silane condensate (C) used is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A).
• the curable composition may contain, together with the silane condensate (C), a silane coupling agent (silane compound) used as an adhesion promoter, a physical property adjuster, a dehydrating agent, etc., which will be described later.
• the silane coupling agent typically corresponds to the above-mentioned silane compound monomer.
• the amount of the silane condensate (C) used is preferably 20 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, still more preferably 50 mass% or more, and particularly preferably 70 mass% or less, based on the total mass of the silane condensate (C) and the mass of the silane coupling agent. From the viewpoint of rapid curing alone, it is preferred that the curable composition does not contain a silane coupling agent.
• the curable composition may contain additives other than the organic polymer (A), the curing catalyst (B), and the silane condensate (C) within a range that does not impair the desired effect.
• the additives include silanol condensation catalysts other than the curing catalyst (B), fillers, adhesion imparting agents, plasticizers, solvents, diluents, thixotropy imparting agents, antioxidants, light stabilizers, ultraviolet absorbers, physical property adjusters, tackifier resins, compounds containing epoxy groups, photocurable substances, oxygen curable substances, epoxy resins, other resins, surface property improvers, foaming agents, curability adjusters, flame retardants, silicates, radical inhibitors, metal deactivators, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.
• the curable composition may contain a silanol condensation catalyst other than the above-mentioned curing catalyst (B) for the purpose of promoting a hydrolysis condensation reaction between reactive silicon groups in the organic polymer (A) and chain extending or crosslinking the polymer.
• silanol condensation catalysts include organotin compounds, metal carboxylates, amine compounds, carboxylic acids, metal alkoxides, and inorganic acids.
• the silanol condensation catalyst may be used in combination of two or more different catalysts.
• the amount of the silanol condensation catalyst used is preferably from 0.001 to 20 parts by weight, more preferably from 0.01 to 15 parts by weight, and particularly preferably from 0.01 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A).
• the curable composition may contain various fillers.
• the fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc oxide, and resin powder; and fibrous fillers such as asbestos, glass fiber, and filaments.
• the resin powder include PVC powder and PMMA powder.
• the amount of the filler used is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight, per 100 parts by weight of the organic polymer (A).
• fillers selected from fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic acid anhydride, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc oxide can be preferably used.
• the amount of fillers used is preferably 1 to 200 parts by weight per 100 parts by weight of organic polymer (A).
• a filler selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloons can be used in an amount of 5 to 200 parts by weight per 100 parts by weight of organic polymer (A) to obtain favorable results.
• the curable composition may contain spherical hollow bodies such as balloons for the purpose of reducing the weight (specific gravity) of the cured product.
• a balloon is a spherical filler with a hollow interior.
• materials for the balloon include inorganic materials such as glass, silase, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, saran, and acrylonitrile.
• the material for the balloon is not limited to these materials.
• the material for the balloon may be a composite material made of an inorganic material and an organic material.
• the material for the balloon may be a laminate of multiple layers.
• the balloon may be used alone or in combination of two or more types.
• the surface of the balloon may be surface-treated, coated, or treated with various surface treatment agents.
• an organic balloon coated with calcium carbonate, talc, titanium oxide, or the like, or an inorganic balloon surface-treated with a silane coupling agent can be used.
• the particle size of the balloons is preferably 3 to 200 ⁇ m, and more preferably 10 to 110 ⁇ m. If the particle size of the balloons is within the above range, the weight of the cured product can be reduced to the desired extent by using an appropriate amount of balloons, and the cured product can be formed while suppressing the occurrence of surface irregularities and reduction in elongation.
• the amount of spherical hollow bodies (balloons) used is preferably 0.01 to 30 parts by weight per 100 parts by weight of the organic polymer (A).
• the lower limit is more preferably 0.1 parts by weight, and the upper limit is more preferably 20 parts by weight. Using an amount of spherical hollow bodies within the above range can improve workability while maintaining the elongation and breaking strength of the cured product.
• the curable composition may contain an adhesion promoter.
• the adhesion promoter include silane coupling agents other than the above-mentioned silane condensate (C).
• Silane coupling agents are compounds having a hydrolyzable silicon group and a functional group other than the hydrolyzable silicon group in the molecule.
• the silane coupling agent can also function as a dehydrating agent, a physical property adjuster, and a dispersibility improver for inorganic fillers.
• the hydrolyzable group in the hydrolyzable silicon group of the silane coupling agent is not particularly limited.
• the hydrolyzable group 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, and a mercapto group.
• a halogen atom, an alkoxy group, an alkenyloxy group, and an aryloxy group are preferred in terms of their high activity.
• a chlorine atom and an alkoxy group are preferred because they are easily introduced into a silane coupling agent.
• 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.
• the compounds that are eliminated by reaction with an ethoxy group and an isopropenyloxy group are ethanol and acetone, respectively, and are preferred in terms of safety.
• the number of hydrolyzable groups bonded to a silicon atom in a silane coupling agent is preferably three in order to ensure good adhesion. In some cases, two is better in order to ensure the storage stability of a curable composition.
• an aminosilane coupling agent having a hydrolyzable silicon group and a substituted or unsubstituted amino group is preferred because of its large adhesiveness improving effect.
• the substituent in the substituted amino group is not particularly limited. Examples of the substituent include an alkyl group, an aralkyl group, and an aryl group.
• aminosilane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisopropoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriethoxysilane, ⁇ -(2-aminoethyl)aminopropylmethyldiethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriisopropoxysilane, ⁇ -(2-(2-aminoethyl)aminoeth,
• ⁇ -aminopropyltrimethoxysilane ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, and ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane are preferred.
• Only one type of aminosilane coupling agent may be used, or two or more types may be used in combination. It has been pointed out that ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane is more irritating than other aminosilanes.
• ⁇ -aminopropyltrimethoxysilane can be used in combination to reduce irritation.
• ⁇ -aminopropyltrimethoxysilane and ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane are preferred.
• silane coupling agents other than aminosilane coupling agents include epoxy group-containing silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane; isocyanate group-containing silane coupling agents such as ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane, ⁇ -isocyanatepropylmethyldiethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, and (isocyanatemethyl)dimethoxy
• gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, and gamma-glycidoxypropylmethyldimethoxysilane are preferred in order to obtain good adhesion in the cured product.
• the above silane coupling agents may be used alone or in combination of two or more.
• the amount of the silane coupling agent used is not particularly limited as long as the desired effect is not impaired.
• the amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A).
• the curable composition may contain a plasticizer.
• a plasticizer makes it possible to adjust the viscosity and slump of the curable composition, and the mechanical properties, such as the tensile strength and elongation, of the cured product.
• plasticizer examples include phthalate compounds other than the phthalate ester (B), 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; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, and dibutyl sebacate.
• phthalate compounds other than the phthalate ester (B) such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, di
• suitable oils include aliphatic polycarboxylic acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters; phosphate compounds such as tricresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil, and epoxy plasticizers such as epoxy benzyl stearate.
• terephthalic acid ester compound is EASTMAN 168 (trade name, manufactured by EASTMAN CHEMICAL).
• non-phthalic acid ester compound is Hexamoll DINCH (trade name, manufactured by BASF).
• alkylsulfonic acid phenyl ester is Mesamoll (trade name, manufactured by LANXESS).
• Polymer plasticizers can also be used. When polymer plasticizers are used, the initial physical properties of the cured product can be maintained for a long period of time compared to when low molecular weight plasticizers are used. Furthermore, the drying properties (paintability) are improved when an alkyd paint is applied to the cured product.
• polymeric plasticizers include vinyl polymers, which are polymers of vinyl monomers; esters of polyalkylene glycols and polyols, such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; polyester plasticizers obtained from dibasic acids, such as sebacic acid, adipic acid, azelaic acid, and phthalic acid, and dihydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; polyether polyols, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, having a number average molecular weight of 500 or more, and even 1,000 or more; derivatives in which the hydroxyl groups of these polyether polyols have been converted to ester groups, ether groups, and the like; polystyrenes, such as polystyrene and poly- ⁇ -methylstyrene
• the polymer plasticizer is preferably compatible with the organic polymer (A).
• polyethers and vinyl polymers are preferred.
• polyethers are used as plasticizers, the surface curing property and deep curing property are improved, and there is no delay in curing after storage.
• polyethers polypropylene glycol is more preferred.
• vinyl polymers are preferred from the viewpoint of compatibility with the polymer (A) and the weather resistance and heat resistance of the cured product.
• acrylic polymers and/or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred.
• the number average molecular weight of the polymer plasticizer is preferably from 500 to 15,000, more preferably from 800 to 10,000, further preferably from 1,000 to 8,000, particularly preferably from 1,000 to 5,000, and most preferably from 1,000 to 3,000.
• the molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow. Specifically, the molecular weight distribution is preferably less than 1.80, more preferably 1.70 or less, even more preferably 1.60 or less, even more preferably 1.50 or less, particularly preferably 1.40 or less, and most preferably 1.30 or less.
• the number average molecular weight of vinyl polymers is measured by the GPC method.
• the number average molecular weight of polyether polymers is measured by the end group analysis method.
• the molecular weight distribution (Mw/Mn) is measured by the GPC method (polystyrene equivalent).
• the polymeric plasticizer may or may not have a reactive silicon group.
• the polymeric plasticizer When the polymeric plasticizer has a reactive silicon group, it acts as a reactive plasticizer and can prevent the migration of the plasticizer from the cured product.
• the polymeric plasticizer has a reactive silicon group, the number of reactive silicon groups is preferably 1 or less on average per molecule, and more preferably 0.8 or less.
• a plasticizer with a reactive silicon group particularly a polyether polymer with a reactive silicon group, it is necessary that its number average molecular weight is lower than that of the organic polymer (A).
• the amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of organic polymer (A).
• the plasticizer may be used alone or in combination of two or more kinds.
• a low molecular weight plasticizer and a polymeric plasticizer may be used in combination. These plasticizers may be blended with the organic polymer (A) when producing the polymer (A).
• the curable composition may contain a solvent or a diluent.
• the solvent and diluent are not particularly limited.
• As the solvent and diluent 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 curable composition is used indoors.
• the above solvents or diluents may be used alone or in combination of two or more kinds.
• the curable composition may contain a thixotropy imparting agent as necessary to prevent sagging and improve workability.
• the thixotropy imparting agent is not particularly limited.
• examples of the thixotropy imparting agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate.
• Examples of the product names include Disparlon 6500, Disparlon 308, Disparlon 6300, Crayvallac SL, and Crayvallac SLT. These thixotropy imparting agents may be used alone or in combination of two or more.
• the amount of the thixotropic agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polymer (A).
• the curable composition may contain an antioxidant (antiaging agent).
• an antioxidant can improve the weather resistance of the cured product.
• examples of the antioxidant include hindered phenol compounds, monophenol compounds, bisphenol compounds, and polyphenol compounds, and hindered phenol compounds are particularly preferred.
• examples of the antioxidant 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); Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, Adeka STAB LA-68 (all manufactured by ADEKA CORPORATION); SANOL LS-2626, SANOL LS-1114, SANOL LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and NOCRAC CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used.
• antioxidants that can be used include SONGNOX 4120, Naugard 445, and OKABEST CLX050. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
• the amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A).
• the curable composition may contain a light stabilizer.
• a light stabilizer can prevent photo-oxidative deterioration of the cured product.
• the light stabilizer include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds.
• a hindered amine-based compound is particularly preferred.
• the amount of the light stabilizer used is preferably from 0.1 to 10 parts by weight, more preferably from 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A). Specific examples of the light stabilizer are described in, for example, JP-A-9-194731.
• a photocurable substance is blended into a curable composition, particularly when an unsaturated acrylic compound is used, it is preferable to use a tertiary amine-containing hindered amine light stabilizer as a hindered amine light stabilizer in order to improve the storage stability of the curable composition, as described in JP-A-5-70531.
• tertiary amine-containing hindered amine light stabilizers include TINUVIN 123, TINUVIN 144, TINUVIN 249, TINUVIN 292, TINUVIN 312, TINUVIN 622LD, TINUVIN 765, TINUVIN 770, TINUVIN 880, TINUVIN 5866, TINUVIN B97, CHIMASSORB 119FL, CHIMASSORB 944LD (all manufactured by BASF); Adeka STAB LA-57, LA-62, LA-63, LA-67, LA-68 (all manufactured by BASF); Examples 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), Nocrac CD (manufactured
• the curable composition may contain an ultraviolet absorber.
• an ultraviolet absorber can improve the surface weather resistance of the cured product.
• ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, salicylate compounds, triazine compounds, substituted tolyl compounds, and metal chelate compounds. Among these, benzotriazole compounds are particularly preferred.
• benzotriazole compounds include Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 1600 (all manufactured by BASF); SONGSORB 3290 (manufactured by SONGWON).
• triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 477, and TINUVIN 1577ED (all manufactured by BASF), and SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON).
• benzophenone compounds include SONGSORB 8100 (manufactured by SONGWON).
• the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A).
• a phenol-based antioxidant or a hindered phenol-based antioxidant in combination with a hindered amine-based light stabilizer and a benzotriazole-based ultraviolet absorber.
• Addworks IBC760 (Clariant) can be used as a product containing a mixture of antioxidants, light stabilizers, and UV absorbers.
• the curable composition may contain a physical property adjuster for adjusting the tensile properties of the cured product, if necessary.
• the physical property adjuster is not particularly limited.
• Examples of the physical property adjuster include alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkyl isopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and ⁇ -glycidoxypropylmethyldiisopropenoxysilane; alkoxysilanes having functional groups such as ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, ⁇ -aminopropyltrime
• compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis have the effect of reducing the modulus of the cured product without worsening the stickiness of the surface of the cured product.
• Compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis are particularly preferred, and compounds that generate trimethylsilanol are particularly preferred.
• Compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include compounds described in JP-A-5-117521.
• derivatives of alkyl alcohols such as hexanol, octanol, and decanol that generate trialkylsilanols such as trimethylsilanol by hydrolysis
• derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as trimethylolpropane, glycerin, pentaerythritol, or sorbitol that generate trialkylsilanols such as trimethylsilanol by hydrolysis, as described in JP-A-11-241029, can be mentioned.
• the derivatives include those of oxyalkylene polymers that produce silicon compounds that produce trialkylsilanols such as trimethylsilanol upon hydrolysis, as described in JP-A-7-258534.Furthermore, polymers having crosslinkable hydrolyzable silicon-containing groups and silicon-containing groups that can become monosilanol-containing compounds upon hydrolysis, as described in JP-A-6-279693, can also be used.
• the physical property adjusting agent is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A).
• the curable composition may contain a tackifier resin for the purpose of increasing the adhesiveness or adhesion of the cured product to a substrate, etc.
• the tackifier resin is not particularly limited, and any tackifier resin that is commonly used in various curable compositions can be used.
• tackifier resins include 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, hydrogenated styrene block copolymers, petroleum resins, hydrogenated petroleum resins, and DCPD resins.
• Examples of petroleum resins include C5 hydrocarbon resins, C9 hydrocarbon resins, and C5C9 hydrocarbon copolymer resins. These may be used alone or in combination of two or more.
• the amount of the 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, based on 100 parts by weight of the polymer (A). By using an amount of the tackifier resin within such a range, a cured product having good adhesion and adhesion to a substrate can be formed.
• the curable composition has an appropriate viscosity, and the handleability of the curable composition is good.
• the curable composition may contain a compound containing an epoxy group.
• 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, epichlorohydrin derivatives, and mixtures thereof.
• Specific examples of the compound having an epoxy group include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate.
• the amount of the compound containing an epoxy group used is preferably 0.5 to 50 parts by weight based on 100 parts by weight of the polymer (A).
• the curable composition may contain an epoxy resin.
• the curable composition containing an epoxy resin is preferably used as an adhesive, particularly as an adhesive for exterior wall tiles.
• the epoxy resin include bisphenol A type epoxy resins and novolac type epoxy resins.
• the ratio of the weight of the polymer (A) to the weight of the epoxy resin is preferably in the range of 100/1 to 1/100, expressed as the weight ratio of (weight of polymer (A))/(weight of epoxy resin).
• the curable composition may contain a curing agent together with the epoxy resin.
• the type of the curing agent is not particularly limited, and a commonly used curing agent can be used.
• the amount of the curing agent used is preferably 0.1 to 300 parts by weight based on 100 parts by weight of the epoxy resin.
• the curable composition may contain a photocurable substance.
• a photocurable substance When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved.
• various compounds such as organic monomers, oligomers, and resins are known.
• many compositions containing a photocurable substance are also known.
• Representative photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, and azido resins.
• unsaturated acrylic compound a monomer, oligomer, or mixture thereof having one or more acrylic unsaturated groups or methacrylic unsaturated groups can be mentioned.
• the amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A).
• the amount of the photocurable substance used falls within this range, a flexible cured product that is excellent in weather resistance and inhibits the occurrence of cracks is easily formed.
• the curable composition may contain an oxygen curing substance.
• oxygen curing substances include unsaturated compounds that can react with oxygen in the air.
• the oxygen curing substance reacts with oxygen in the air to form a cured film near the surface of the cured product. By forming a cured film on the surface of the cured product, stickiness and adhesion of dirt and dust to the surface of the cured product can be prevented.
• oxygen curing substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying drying oils; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, or C5 to C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, or 1,3-pentadiene. These may be used alone or in combination of two or more types.
• the amount of the oxygen-curing substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A).
• the oxygen-curing substance is used in an amount within this range, the surface is less likely to be contaminated by dirt or dust, and a cured product having excellent mechanical properties such as tensile properties is easily formed.
• the oxygen-curing substance is preferably used in combination with a photocuring substance.
• the curable composition can be prepared as a one-component type in which all ingredients are mixed in advance, sealed, and stored, and then cured by moisture in the air after application.
• a one-liquid type curable composition can be prepared by mixing the organic polymer (A), the condensation catalyst (B), and the silane condensate (C) with the above-mentioned optional ingredients as necessary.
• the curing agent composition can also be prepared as a two-component type in which a compounding material as a curing agent in which the curing catalyst (B), the silane condensate (C), and ingredients such as a filler, a plasticizer, and water are mixed with a composition containing a separately prepared organic polymer (A) before use.
• the one-component type is preferred.
• the curable composition is of one-component type, all the components are blended in advance, and therefore, it is preferable that the components containing water are dehydrated and dried before use, or dehydrated under reduced pressure during blending and kneading.
• the storage stability can be further improved by adding an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane.
• an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane.
• the amount of the dehydrating agent, particularly a silicon compound capable of reacting 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 polymer (A).
• the curable composition can be used as a construction sealant, industrial adhesive, waterproof coating composition, adhesive raw material, etc.
• the curable composition can also be used as a sealant for buildings, ships, automobiles, roads, etc.
• the curable composition can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer. Therefore, the curable composition can also be used as various types of sealing compositions and adhesive compositions.
• the curable composition can also be used as a contact adhesive in addition to ordinary adhesives.
• the curable composition is also useful as a food packaging material, a cast rubber material, a material for molding, and a paint.
• the cured product of the above curable composition exhibits low water absorption. Therefore, the above curable composition and its cured product are particularly suitable for use as waterproof materials, such as sealants, waterproof adhesives, and waterproof coatings.
• the curable composition Prior to curing, the curable composition is formed into a desired shape by a method such as coating, casting, or filling.
• the hardenable composition that has been applied, cast, or filled and shaped is then hardened under the desired environment, such as room temperature and humidity.
• a curable composition comprising an organic polymer (A), a curing catalyst (B), and a silane condensate (C),
• the organic polymer (A) is represented by the following formula (1): -SiR 1 X 2 (1)
• R 1 is a hydrocarbon group having 1 to 20 carbon atoms
• X is a hydroxyl group or a hydrolyzable group, and the two Xs may be the same or different.
• the curing catalyst (B) contains an amidine compound (b1) and a titanium compound (b2)
• the amidine compound (b1) is represented by the following formula (2):
• R 2 N CR 3 -NR 4 2 (2)
• R 2 , R 3 , and R 4 are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the two R 4s may be the same or different, and any two of R
• ⁇ 3> The curable composition according to ⁇ 1> or ⁇ 2>, wherein the silane condensate (C) is a condensate of at least one kind of trimethoxysilane selected from vinyltrimethoxysilane, amino group-containing trimethoxysilane, and alkyltrimethoxysilane.
• d represents 0 or an integer of 1 to 3.
• ⁇ 5> The curable composition according to any one of ⁇ 1> to ⁇ 4>, wherein the main chain structure of the organic polymer (A) is polyoxyalkylene.
• ⁇ 6> The curable composition according to any one of ⁇ 1> to ⁇ 5>, wherein the amidine compound (b1) is DBU (1,8-diazabicyclo[5.4.0]-7-undecene).
• a weight ratio (b2)/(b1) of the titanium compound (b2) to the amidine compound (b1) is 1.0 to 10.
• the number average molecular weight is a GPC molecular weight measured under the following conditions.
• Liquid delivery system Tosoh HLC-8120GPC
• Column Tosoh TSK-GEL H type
• Solvent THF
• the terminal group converted molecular weight in the examples is the molecular weight calculated by determining the hydroxyl value according to the measurement method of JIS K 1557 and the iodine value according to the measurement method of JIS K 0070, taking into consideration the structure of the organic polymer.
• the degree of branching determined by the polymerization initiator used was taken into consideration with regard to the structure of the organic polymer.
• the average number of reactive silicon groups per terminal of the organic polymer shown in the examples was calculated by measurement using 1 H-NMR (measured in CDCl 3 solvent using AVANCE III HD-500 manufactured by Bruker).
• Preparation Example 1 Organic polymer (A-1))
• a 1/1 (weight ratio) mixture of polyoxypropylene diol having a molecular weight of about 2,000 and polyoxypropylene triol having a molecular weight of 3,000 is used as an initiator, and propylene oxide is polymerized in the presence of zinc hexacyanocobaltate glyme complex catalyst.
• a hydroxyl-terminated polypropylene oxide having a number average molecular weight of 19,000 was obtained.
• a methanol solution of 1.2 molar equivalents of NaOMe was added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene.
• allyl chloride was further added to the reaction solution to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure.
• polypropylene oxide with an allyl group at the end and a number average molecular weight of about 19,000 was obtained.
• 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene were mixed with 300 parts by weight of n-hexane and 300 parts by weight of water, and the mixture was stirred.
• allyl polymer 100 parts by weight of the obtained allyl polymer, 150 ppm of an isopropanol solution of platinum vinyldisiloxane complex with a platinum content of 3 wt% was added as a catalyst. Next, 0.7 molar equivalents of dimethoxymethylsilane were added relative to the allyl groups of the allyl polymer, and the allyl group terminals and dimethoxymethylsilane were reacted at 90°C for 5 hours to obtain dimethoxymethylsilyl-terminated polypropylene oxide (A-1). The number of dimethoxymethylsilyl groups per polymer chain terminal was approximately 0.7.
• Preparation Example 2 Organic polymer (A-2)) Using polyoxypropylene diol having a molecular weight of about 2,000 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polypropylene oxide having a number average molecular weight of 28,500.
• allyl polymer To 100 parts by weight of the obtained allyl polymer, 150 ppm of an isopropanol solution of platinum vinyldisiloxane complex with a platinum content of 3 wt % was added as a catalyst. Next, 0.8 molar equivalents of dimethoxymethylsilane were added relative to the allyl groups of the allyl polymer, and the allyl group terminals and dimethoxymethylsilane were reacted at 90°C for 5 hours to obtain dimethoxymethylsilyl-terminated polypropylene oxide (A-2). The number of dimethoxymethylsilyl groups per polymer chain terminal was about 1.5.
• Preparation Example 3 Organic polymer (A-3)) Using polyoxypropylene triol with a molecular weight of about 3,000 as an initiator, propylene oxide is polymerized with zinc hexacyanocobaltate glyme complex catalyst to produce a hydroxyl group having a branched structure in the main chain and a number average molecular weight of about 25,000. Terminal polypropylene oxide was obtained.
• the allyl polymer was purified in the same manner as in Preparation Example 1. 150 ppm of an isopropanol solution of platinum vinyldisiloxane complex with a platinum content of 3 wt% was added as a catalyst to 100 parts by weight of the obtained allyl polymer. Next, 0.7 molar equivalents of dimethoxymethylsilane were added to the allyl groups of the allyl polymer, and the allyl group terminals and dimethoxymethylsilane were reacted at 90°C for 5 hours to obtain dimethoxymethylsilyl-terminated polypropylene oxide (A-3). The number of dimethoxymethylsilyl groups per polymer chain terminal was approximately 0.7.
• Preparation Example 4 Organic polymer (A-4)) Using polyoxypropylene triol having a molecular weight of about 4,500 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 14,300.
• a methanol solution of 1.2 molar equivalents of NaOMe was added to the hydroxyl groups of the obtained hydroxyl-terminated polypropylene oxide.
• allyl chloride was further added to the reaction solution to convert the terminal hydroxyl groups to allyl groups.
• an allyl polymer with an allyl group at the end and a number average molecular weight of about 14,300 was obtained.
• the allyl polymer was purified in the same manner as in Preparation Example 1.
• 150 ppm of an isopropanol solution of platinum vinyldisiloxane complex with a platinum content of 3 wt % was added as a catalyst to 100 parts by weight of the obtained allyl polymer.
• the number of dimethoxymethylsilyl groups per polymer chain terminal was about 0.8.
• Preparation Example 5 Organic polymer (A-5)) 22 parts by weight of isobutyl alcohol was placed in a four-neck flask equipped with a stirrer, and the mixture was heated to 90° C. under a nitrogen atmosphere. 20.1 parts by weight of stearyl methacrylate, 4.5 parts by weight of 3-(dimethoxymethylsilyl)propyl methacrylate, and 1.9 parts by weight of 2,2'-azobis(2-methylbutyronitrile) were dissolved in 17. A mixed solution in which 0.2 parts by weight of 2,2'-azobis(2-methylbutyronitrile) was dissolved in 1.8 parts by weight of isobutyl alcohol was added dropwise over a period of 5 hours.
• Preparation Example 6 Organic polymer (A-6)) Using polyoxypropylene diol having a molecular weight of about 2,000 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 16,000.
• a methanol solution of 1.2 molar equivalents of NaOMe was added to the hydroxyl groups of the obtained hydroxyl-terminated polypropylene oxide.
• allyl chloride was further added to the reaction solution to convert the terminal hydroxyl groups to allyl groups.
• an allyl polymer with an allyl group at the end and a number average molecular weight of about 14,300 was obtained.
• the allyl polymer was purified in the same manner as in Preparation Example 1.
• 150 ppm of an isopropanol solution of platinum vinyldisiloxane complex with a platinum content of 3 wt % was added as a catalyst to 100 parts by weight of the obtained allyl polymer.
• dimethoxymethylsilyl-terminated polypropylene oxide A-6
• the number of dimethoxymethylsilyl groups per polymer chain terminal was about 0.6.
• Organic Polymer (A) ((A-1) (Organic Polymer (A-1) Obtained in Preparation Example 1)) Colloidal calcium carbonate (product name: Hakuenka CCR, manufactured by Shiraishi Kogyo Co., Ltd.) Heavy calcium carbonate (product name: Whiten SB, manufactured by Bihoku Funka Kogyo Co., Ltd.) Plasticizer (product name: Hexamoll DINCH, manufactured by BASF) Pigment (product name: Typak R820, manufactured by Ishihara Sangyo Kaisha, Ltd.) Thixotropic agent (product name: Crayvallc SLT, manufactured by ARKEMA) Antioxidant (product name: Irganox 1010, manufactured by BASF) Ultraviolet absorber (product name: Tinuvin 326, manufactured by BASF) Light stabilizer (product name: Tinuvin 770, manufactured by BASF) Amidine compound (b1) (DBU (1,8-diazabicyclo[5.4.0]undec-7
• the curable composition obtained above was filled into a moisture-proof container and stored for 7 days under an atmosphere of 23°C and 50% relative humidity. Under an atmosphere of 23°C and 50% relative humidity, the curable composition was filled into a mold of about 5 mm thickness, and the surface of the curable composition was adjusted to a flat surface. The time when the surface was adjusted to a flat surface was defined as the curing start time.
• the curable composition in the mold was touched with a spatula, and the time when the mixture 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.
• the components in Table 2 are as follows.
• As the colloidal calcium carbonate Hakuenka CCR (manufactured by Shiraishi Kogyo Co., Ltd.) was used.
• Whiten SB (manufactured by Bihoku Funka Kogyo Co., Ltd.) was used.
• plasticizers Hexamoll DINCH (manufactured by BASF), DINP (diisononyl phthalate, manufactured by J-Plus), and Actcoal P-23 (manufactured by Mitsui Chemicals SKC Polyurethanes, Inc.) were used.
• Typec R820 (manufactured by Ishihara Sangyo Kaisha, Ltd.) was used.
• Crayvallc SLT (ARKEMA) was used.
• Irganox 1010 (manufactured by BASF) was used.
• Tinuvin 326 manufactured by BASF
• Tinuvin 770 manufactured by BASF
• amidine compound (b1) DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
• titanium compound (b2) As the titanium compound (b2), TC-750 (bis(ethylacetoacetate)diisopropoxytitanium), manufactured by Matsumoto Fine Chemical Co., Ltd.), Tyzor KE-6 (bis(ethylacetoacetate)diisobutoxytitanium), manufactured by Dorff Ketal, Tyzor 9000 (tetra tert-butoxytitanium), manufactured by Dorff Ketal, and Ti(O i Pr) 4 (tetraisopropoxytitanium), manufactured by Tokyo Chemical Industry Co., Ltd.) were used.
• Composite 1 is the composite 1 obtained in Synthesis Example 1.
• Composite 2 is the composite 2 obtained in Synthesis Example 2.
• Composite 3 is the composite 3 obtained in Synthesis Example 3.
• silane condensate (C) Dynasylan 6490 (manufactured by Evonik Corporation) and Dynasylan 1146 (manufactured by Evonik Corporation) were used.

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