WO2016027475A1 - Composition durcissable et corps durci obtenu à partir de celle-ci - Google Patents

Composition durcissable et corps durci obtenu à partir de celle-ci Download PDF

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WO2016027475A1
WO2016027475A1 PCT/JP2015/004229 JP2015004229W WO2016027475A1 WO 2016027475 A1 WO2016027475 A1 WO 2016027475A1 JP 2015004229 W JP2015004229 W JP 2015004229W WO 2016027475 A1 WO2016027475 A1 WO 2016027475A1
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curable composition
metal alkoxide
modified polysiloxane
titanium
group
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PCT/JP2015/004229
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English (en)
Japanese (ja)
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裕介 青木
和代 宮田
幹人 狩野
修平 中村
義身 田中
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国立大学法人三重大学
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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives 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
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin 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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a curable composition and a cured product obtained by curing the composition.
  • polyorganosiloxane compositions have been used for adhesives and sealing materials because they exhibit excellent weather resistance and durability when cured.
  • a cured product of a polyorganosiloxane composition tends to require higher strength.
  • a polyorganosiloxane composition in which a filler made of an inorganic or organic compound is mixed is known (see Patent Document 1).
  • organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin dilaurate are widely used as catalysts.
  • organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin dilaurate are widely used as catalysts.
  • amine compounds and carboxylic acid compounds see Patent Document 2
  • relatively safe bismuth compounds (patents)
  • Patent Document 4 a silanol condensation catalyst
  • these catalysts have not yet replaced the existing organotin compound-based catalysts.
  • the present invention has been made in view of such problems, and an object of the present invention is to obtain a curable composition that is one-part, excellent in curing characteristics, and high in workability, and a cured body obtained by curing the composition.
  • One form of the present invention for achieving the above object is a curing catalyst comprising (A) a crosslinkable silyl group-containing resin and (B) a combination of a titanium chelate and a guanidine compound (B1) or an organotin compound (B2). And (C) a metal alkoxide-modified polysiloxane.
  • C there is further provided (C) a curable composition in which the metal alkoxide-modified polysiloxane has methoxysilane or ethoxysilane at one end or both ends of the main chain of the organopolysiloxane, or one side or both sides of the side chain. It is.
  • a metal alkoxide-modified polysiloxane obtained by modifying the organopolysiloxane with methoxysilane or ethoxysilane, or polydiphenyldimethyl obtained by modifying methoxysilane or ethoxysilane. It is a curable composition to be siloxane.
  • the (C) metal alkoxide-modified polysiloxane contains a methoxysilane having a number average molecular weight (Mn) of 150 or more or an ethoxysilane having a number average molecular weight (Mn) of 750 or more. It is a thing.
  • Another embodiment of the present invention is a curable composition using methoxysilane as a silane coupling agent having tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane or methoxy group.
  • the (C) metal alkoxide-modified polysiloxane is a curable composition containing ethoxysilane having a number average molecular weight (Mn) of 1,300 or more.
  • Another embodiment of the present invention also includes (C) a surplus metal alkoxide that forms a metal alkoxide-modified polysiloxane, and the theoretical metal alkoxide-modified polysiloxane calculated from the amount of metal alkoxide is 100%.
  • the ratio of the actual (C) metal alkoxide-modified polysiloxane is 90 to 99.9%.
  • Another embodiment of the present invention is a curable composition having the above-mentioned ratio of 93 to 99.9%.
  • Another embodiment of the present invention is a curable composition in which (C) the metal alkoxide-modified polysiloxane does not detect a low molecular component having a weight average molecular weight (Mw) of 400 or less in GPC measurement.
  • Mw weight average molecular weight
  • Another embodiment of the present invention is a curable composition obtained by adding 0.1 to 5 mol of a guanidine compound to 1 mol of a titanium chelate.
  • Another embodiment of the present invention is a curable composition obtained by adding 2 to 5 mol of a guanidine compound to 1 mol of a titanium chelate.
  • Another embodiment of the present invention is also a curable composition
  • a curable composition comprising (C) a metal alkoxide-modified polysiloxane added with more than 1 mole of metal alkoxide or a hydrolysis condensate thereof per mole of organopolysiloxane. is there.
  • the curing catalyst is a combination of a titanium chelate and a guanidine compound (B1), and the guanidine compound is 1,1,3,3-tetramethylguanidine and 1- (o-tolyl).
  • a curable composition comprising at least one of biguanides.
  • One embodiment of the present invention is a cured body obtained by curing any of the above-described curable compositions.
  • the present invention it is possible to obtain a curable composition that is one-part, excellent in curing characteristics, and high in workability, and a cured body obtained by curing the composition.
  • FIG. 1 shows a schematic diagram of a terminal modification pattern of an assumed alkoxysilane terminal-modified polysiloxane.
  • FIG. 2 shows the adhesive strength (after 1 day and after 7 days) of Example 1 and Comparative Example 3 in comparison.
  • FIG. 3 shows a comparison of mechanical properties (elastic modulus, tensile fracture strength, elongation) of Example 1 and Comparative Example 3.
  • FIG. 4 shows a comparison of the adhesive strength (after 1 day and after 7 days) of Example 1, Example 2 and Comparative Example 1.
  • FIG. 5 shows the mechanical properties (elastic modulus, tensile fracture strength, elongation) of Example 1, Example 2 and Comparative Example 1 in comparison.
  • FIG. 1 shows a schematic diagram of a terminal modification pattern of an assumed alkoxysilane terminal-modified polysiloxane.
  • FIG. 2 shows the adhesive strength (after 1 day and after 7 days) of Example 1 and Comparative Example 3 in comparison.
  • FIG. 3 shows a comparison of mechanical properties (e
  • FIG. 6 shows a comparison of the adhesive strength (after 1 day and after 7 days) of Example 7 and Comparative Example 6.
  • FIG. 7 shows the mechanical properties (elastic modulus, tensile fracture strength, elongation) of Example 7 and Comparative Example 6 in comparison.
  • FIG. 8 shows a GPC curve (8A) before denaturation and a curve (8B) before and after separation of the waveform of the ES peak intensity.
  • FIG. 9 is a chart (9A) showing a change in GPC of an alkoxysilane-end-modified polysiloxane (ES45-PDPDMS) having a modification rate of 91%, a modification rate of 93%, and a modification rate of 97% before the modification treatment and up to a modification rate of 97%.
  • a chart (9B) showing a comparison of the GPCs of the low molecular component reduction treatment after the denaturation treatment and the low molecular component reduction treatment is shown.
  • Curable composition which concerns on this embodiment is (A) a crosslinkable silyl group-containing resin; (B) a curing catalyst comprising a combination of a titanium chelate and a guanidine compound (B1) or an organotin compound (B2); (C) a metal alkoxide-modified polysiloxane; including.
  • the “including” or “comprising” state is broadly interpreted to include not only a mere mixed state but also a partially reacting state.
  • the crosslinkable silyl group-containing resin (B) the curing catalyst, and (C) the metal alkoxide-modified polysiloxane, (D) other additives will be described in detail.
  • the crosslinkable silyl group-containing resin is a resin having a silicon-containing group having a hydrolyzable functional group bonded to a silicon atom or a silanol group capable of causing a condensation reaction.
  • the hydrolyzable group is not particularly limited, and examples thereof include 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. Groups and the like.
  • the crosslinkable silyl group-containing resin has the following general formulas (1), (2), and (3) (“Chemical Formula 1”, “Chemical Formula 2”, and “Chemical Formula 3”, respectively).
  • R 1 , R 2 and R 3 in the functional groups of the following general formulas (1) to (3) are the same or different from each other, hydrogen, an alkyl group having 1 or more carbon atoms, or an aryl group An aralkyl group, a triorganosiloxy group, an alkenyl group or a cycloalkyl group.
  • Specific examples of R 1 , R 2 and R 3 in the above general formula include hydrogen, methyl group, ethyl group, cyclohexyl group, phenyl group, benzyl group, trimethylsiloxy group, triphenylsiloxy group, methylene group and ethylene group. And cyclopropyl group. Of these exemplified groups, a methyl group is particularly preferred.
  • X and Y may be the same as or different from each other, and are groups other than alkoxy groups such as hydrogen and hydrocarbon groups.
  • Specific examples of the crosslinkable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group.
  • a highly active trimethoxysilyl group, triethoxysilyl group, and dimethoxymethylsilyl group are more preferable, and a trimethoxysilyl group is particularly preferable.
  • crosslinkable silyl group-containing resin examples include silyl group-containing polyether, silyl group-containing polyester, silyl group-containing organic polysiloxane polymer, silyl group-containing vinyl polymer, silyl group-containing polyester-modified vinyl polymer, silyl group -Containing diallyl phthalate polymers, silyl group-containing diaryl phthalate polymers, silyl group-containing polyisobutylenes, silyl group-containing ethylene / ⁇ -olefin copolymers, and mixtures thereof.
  • the crosslinkable silyl group-containing resin is a silyl group-containing polyether
  • the main chain polyether is made of ethylene oxide, propylene oxide, butene oxide, tetrahydrofuran, or the like as a raw material, and is subjected to cationic polymerization or anionic polymerization. What is manufactured using can be illustrated suitably.
  • the crosslinkable silyl group-containing resin is a silyl group-containing polyester
  • a carboxylic acid such as maleic acid, succinic acid, glutaric acid, adipic acid, or phthalic acid, its anhydride, its ester or halide
  • Polyester polyols prepared by reacting with a stoichiometric excess of polyols such as ethylene glycol, propylene glycol and glycerin, or polyesters such as lactone polyols obtained by ring-opening polymerization of lactones as the main chain
  • polyols such as ethylene glycol, propylene glycol and glycerin
  • lactone polyols obtained by ring-opening polymerization of lactones as the main chain
  • crosslinkable silyl group-containing resin is a silyl group-containing organic polysiloxane polymer
  • a resin having a main chain connected by a siloxane bond Si—O—Si bond
  • Si—O—Si bond a resin having a main chain connected by a siloxane bond
  • crosslinkable silyl group-containing resins examples include “Kaneka Silyl EST280” (a crosslinkable silyl group-containing polyether polymer belonging to a modified silicone resin) and “Kaneka MS Polymer” manufactured by Kaneka Corporation. "S303” (silyl terminal-modified polyether), “X-21-5841” (silyl group-modified polydimethylsiloxane) manufactured by Shin-Etsu Silicone Co., Ltd., “ARUFON” (alkoxysilyl group-containing acrylic polymer manufactured by Toa Gosei Co., Ltd.) ).
  • Titanium chelates are commercially available, and can be prepared using, for example, titanium alkoxide and a bidentate organic chelating agent.
  • Titanium alkoxides include titanium tetramethoxide, titanium tetraethoxide, titanium tetraallyl oxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetraisobutoxide, titanium tetra sec-butoxide, Titanium tetra t-butoxide, titanium tetra n-pentyl oxide, titanium tetracyclopentyl oxide, titanium tetrahexyl oxide, titanium tetracyclohexyl oxide, titanium tetrabenzyl oxide, titanium tetraoctyl oxide, titanium tetrakis (2-ethylhexyl oxide), titanium tetradecyl Oxide, Titanium tetradodecyl oxide, Titanium Tetrastearyl oxide, titanium tetrabutoxide dimer, titanium tetradecyl Oxide, Titan
  • titanium alkoxides may be used alone or in combination. Among these, a titanium alkoxide containing an alkoxide group having 1 to 12 carbon atoms is more preferable, and a titanium alkoxide containing an alkoxide group having 1 to 6 carbon atoms is more preferable. Moreover, these oligomers can also be used. More preferred examples of the titanium alkoxide are titanium tetraethoxide, titanium tetrapropoxide, or titanium tetrabutoxide. From the viewpoint of easy handling, availability and curability, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, and titanium tetra t-butoxide are preferred.
  • bidentate organic chelating agent As the bidentate organic chelating agent for stabilizing the titanium alkoxide, the general formula: R 4 (CO) —CH 2 —X (R 4 ; alkyl group, alkoxy group, aryl group, X: carbonyl group, An active methylene compound represented by an electron-withdrawing group such as a cyano group) can be preferably used. Examples of the active methylene compound include acetylacetone, malonic acid diester, acetoacetate ester, cyanoacetate ester, and Meldrum's acid.
  • malonic acid diesters examples include dimethyl malonate, diethyl malonate, diisopropyl malonate, di-n-propyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, ethyl n-butyl malonate, methyl malonate n-butyl, ethyl t-butyl malonate, methyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzylmethyl malonate, ethyl phenyl malonate, t-butylphenyl malonate, isopropylidene Examples include malonate.
  • acetoacetate examples include methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, t-butyl acetoacetate, n-butyl acetoacetate, benzyl acetoacetate, phenyl acetoacetate and the like. it can.
  • cyanoacetic acid esters examples include methyl cyanoacetate, ethyl cyanoacetate, n-propyl cyanoacetate, i-propyl cyanoacetate, n-butyl cyanoacetate, i-butyl cyanoacetate, t-butyl cyanoacetate, benzyl cyanoacetate, Examples include methyl diphenyl cyanoacetate, ethyl diphenyl cyanoacetate, methyl 2-methylphenyl cyanoacetate, and ethyl 2-methylphenyl cyanoacetate. Of these active methylene compounds, ethyl acetoacetate and acetylacetone are particularly preferred.
  • guanidine compound examples include 1,1,2-trimethylguanidine, 1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,2,3-pentamethylguanidine.
  • guanidine compounds 1,1,3,3-tetramethylguanidine and 1- (o-tolyl) biguanide are particularly preferable.
  • a suitable addition amount of the guanidine compound is 0.1 to 5 mole ratio, more preferably 0.2 to 5 mole ratio, and most preferably 2 to 5 mole ratio with respect to the titanium chelate.
  • Organotin compound examples include monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra-n-octyltin, tetra-n-butyltin, and dibutyl.
  • Tin oxide dibutyltin diacetate, dibutyltin dioctate, dibutyltin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound , Dioctyltin salt and silicate compound, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylmalate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis Benzyl malate), dibutyltin bis (stearyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (o-phenylphenoxide
  • the addition amount of the curing catalyst (B) is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 3 to 7 parts by weight with respect to 100 parts by weight of the crosslinkable silyl group-containing resin (A). It is.
  • the curing catalyst (B) is composed of a plurality of types, some types of curing catalysts (B) are mixed in advance with the crosslinkable silyl group-containing resin (A), and the remaining types A curing catalyst (B) can be mixed.
  • plural kinds of curing catalysts (B) may be mixed in advance, and the crosslinkable silyl group-containing resin (A) may be mixed there.
  • metal alkoxide-modified polysiloxane is a polymer in which one end or both ends of the main chain of polysiloxane or the side chain of polysiloxane is modified with a metal alkoxide or a hydrolysis condensate thereof.
  • Polysiloxanes having one or both ends of the main chain modified with metal alkoxide are represented by general formulas (4) (“Chemical Formula 4”), (5) (“Chemical Formula 5”).
  • the metal alkoxide terminal-modified polysiloxane having the structure of the general formulas (4) to (6) is a silicone polymer obtained by modifying one end of a main chain connected by a siloxane bond with a metal alkoxide or a hydrolysis condensate thereof.
  • the metal alkoxide terminal-modified polysiloxane having the structure of the general formulas (7) to (9) is a silicone polymer obtained by modifying both ends of the main chain connected by a siloxane bond with a metal alkoxide or a hydrolysis condensate thereof.
  • the metal (M) of the metal alkoxide silicon, titanium, aluminum, barium, bismuth, boron, calcium, iron, gallium, hafnium, indium, potassium, lanthanum, lithium, magnesium, sodium, niobium, lead, polonium, phosphorus, Tin, strontium, tantalum, vanadium, tungsten, yttrium, zirconium and the like can be exemplified, and in particular, silicon, titanium, zirconium, aluminum and the like can be more suitably exemplified.
  • the metal alkoxide is more preferably an alkoxysilane, and most preferably methoxysilane or ethoxysilane.
  • R 7 , R 8 , R 9 , R 10 and R 11 may be the same or different from each other, and may be an alkyl group having 1 or more carbon atoms, an aryl group, or an aralkyl. Group, a triorganosiloxy group, an alkenyl group or a cycloalkyl group.
  • R 7 , R 8 , R 9 , R 10 and R 11 include methyl group, ethyl group, cyclohexyl group, phenyl group, benzyl group, trimethylsiloxy group, triphenylsiloxy group, methylene group, ethylene group, A cyclopropyl group and a cyclohexyl group can be mentioned.
  • X and Y may be the same as or different from each other, and are groups other than alkoxy groups such as hydrogen and hydrocarbon groups.
  • n is an integer of 2 or more.
  • m is an integer of 1 or more.
  • R 7 and R 8 are other than those R 7 R 8 SiO has n pieces linked, R 7a R 8a SiO is p pieces, even those that R 7b R 8b SiO is (n-p) pieces connected good.
  • p is an integer of 1 or more, and is smaller than n.
  • R 7a and R 8a are same as R 7 and R 8, identical a good number of 1 or more carbon atoms be different even if an alkyl group with one another, an aryl group, an aralkyl group, triorganosiloxy groups, alkenyl groups or cycloalkyl It is a group.
  • R 7b and R 8b The same applies to R 7b and R 8b .
  • the combination of R 7a and R 8a is not the same as the combination of R 7b and R 8b .
  • the functional group modified with the alkoxide is not a single end or both ends of the main chain of the polysiloxane, but a part of the side chain of the polysiloxane (R 7 , R 8 ) or It may be introduced to all.
  • the metal alkoxide-modified polysiloxane has a general formula (11) (“Chemical Formula 10”) represented by General Formula (10) (“Chemical Formula 10”) on one or both ends of the main chain of the organopolysiloxane or at least one side chain. 11 ”), (12) (“ Chemical Formula 12 ”) or (13) (“ Chemical Formula 13 ”), and modified with a metal alkoxide or a hydrolysis condensate thereof.
  • R 7 , R 8 , R 9 , R 10 and R 11 ; X and Y; n and m are the same as those in formulas (4) to (9).
  • organopolysiloxane for example, polydialkyl siloxane, polydiaryl siloxane, polyalkylaryl siloxane and the like are preferably mentioned. More specifically, polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, And polydiphenyldimethylsiloxane. One of these may be used, or two or more may be used in combination.
  • the number average molecular weight (Mn) of the organopolysiloxane is preferably in the range of 100 to 100,000, more preferably in the range of 1,000 to 50,000.
  • alkoxysilane which modifies at least one terminal or side chain of the organopolysiloxane and at least a part thereof, but alkoxysilane is particularly preferable.
  • alkoxysilanes tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-but
  • alkoxysilanes may be used, or two or more types may be used in combination.
  • alkoxysilane tetramethoxysilane and trimethoxymethylsilane are particularly preferable.
  • organopolysiloxane polydimethylsiloxane and polydiphenyldimethylsiloxane are particularly preferable.
  • a polydimethylsiloxane or polydiphenyldimethylsiloxane having a terminal modified with methoxysilane can be suitably produced.
  • the molecular weight of alkoxysilane is preferably in the range of 90 to 1,000, more preferably in the range of 100 to 300.
  • alkoxysilane hydrolysis condensate examples include polymethyl silicate, polyethyl silicate, polypropoxy silicate, polybutoxy silicate, and polybutoxy silicate.
  • One of these alkoxysilane hydrolysis condensates may be used, or two or more may be used in combination.
  • polyethyl silicate is particularly preferable.
  • the organopolysiloxane is preferably polydimethylsiloxane or polydiphenyldimethylsiloxane as described above.
  • Combining the preferred hydrolyzed condensate of alkoxysilane with the preferred organopolysiloxane can suitably produce polydimethylsiloxane or polydiphenyldimethylsiloxane having a terminal modified with ethoxysilane.
  • the number average molecular weight (Mn) of the hydrolysis-condensation product of alkoxysilane is preferably in the range of 300 to 30,000, more preferably in the range of 500 to 5,000.
  • the polymer of metal alkoxide which is at least one terminal or side chain of the main chain of the organopolysiloxane and modifies at least a part thereof preferably has a number average molecular weight (Mn) of 150.
  • Mn number average molecular weight
  • the number average molecular weight (Mn) of ethoxysilane is preferably 1,000 or more, and more preferably 1,300 or more.
  • the methoxysilane for modifying the organopolysiloxane may be dimethyldimethoxysilane or a silane coupling agent having a methoxy group in addition to the above-mentioned tetramethoxysilane or methyltrimethoxysilane.
  • alkoxysilane As an example of the metal alkoxide, alkoxysilane has been described. For example, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetra-n-butoxytitanium, etc. using titanium as a metal.
  • Tetraalkoxytitaniums Tetraalkoxytitaniums; methyltrimethoxytitanium, methyltriethoxytitanium, ethyltrimethoxytitanium, ethyltriethoxytitanium, n-propyltrimethoxytitanium, n-propyltriethoxytitanium, i-propyltrimethoxytitanium, i-propyl Triethoxytitanium, n-butyltrimethoxytitanium, n-butyltriethoxytitanium, n-pentyltrimethoxytitanium, n-hexyltrimeth Titanium, n-heptyltrimethoxytitanium, n-octyltrimethoxytitanium, vinyltrimethoxytitanium, vinyltriethoxytitanium, cyclohexyltrimethoxy
  • the addition amount of the metal alkoxide-modified polysiloxane (C) is 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 to 3 parts by weight with respect to 100 parts by weight of the crosslinkable silyl group-containing resin (A). 10 parts by mass.
  • the metal alkoxide-modified polysiloxane (C) is preferably formed by adding more than 1 mole of metal alkoxide to 1 mole of organopolysiloxane. This is because at least part of the organopolysiloxane can include those modified at both ends of the main chain or both sides of the side chain with a metal alkoxide or a hydrolysis condensate thereof, which contributes to an improvement in adhesive strength. is there.
  • the metal alkoxide-modified polysiloxane there may be an excess of metal alkoxide in excess of that forming the metal alkoxide-modified polysiloxane.
  • the excess metal alkoxide is preferably a small amount.
  • the ratio of the actual metal alkoxide-modified polysiloxane (referred to as the modification rate) when the theoretical metal alkoxide-modified polysiloxane calculated from the amount of metal alkoxide in the cured composition is 100% is in the range of 90 to 100%. Further, it is preferably in the range of 93 to 100%.
  • the modification rate is preferably in the range of 90 to 99.9%, more preferably in the range of 93 to 99.9%.
  • the “denaturation rate” is calculated by the following method.
  • the amount of the metal alkoxide (for example, ethoxysilane) before the modification treatment that modifies at least one terminal or side chain of the main chain of the organopolysiloxane and at least a part thereof is modified with respect to the amount of the modified organopolysiloxane (for example, Modified PDMS)
  • the amount of metal alkoxide after the synthesis treatment is estimated by gel permeation chromatography (GPC).
  • the modification rate of the metal alkoxide-modified organopolysiloxane is determined from the amount of metal alkoxide consumed.
  • the increase / decrease in the modification rate can be adjusted by increasing / decreasing the heating temperature during the modification treatment or by increasing / decreasing the heating time under a constant temperature.
  • the metal alkoxide-modified polysiloxane is preferably one in which a low molecular component having a weight average molecular weight (Mw) of 400 or less is not detected by GPC measurement.
  • Mw weight average molecular weight
  • the reduction of such low molecular components is performed, for example, by heating at 90 to 120 ° C., more preferably 95 to 110 ° C. in a flow of an inert gas (for example, dry nitrogen gas) after the modification treatment. It is preferable that a low molecular component with Mw of 400 or less is not detected, but a low molecular component with Mw ⁇ 300 or Mw ⁇ 200 may not be detected.
  • Light stabilizer may be added to the curable composition according to this embodiment.
  • the light stabilizer is effective in improving the weather resistance of the resin or imparting thermal stability. Since the light stabilizer and the ultraviolet absorber described below may reduce the function of the titanium chelate as a curing catalyst, a guanidine compound can be added to effectively prevent the catalyst function from decreasing. Furthermore, when metal alkoxide modified polysiloxane is added, the adhesive strength between the cured body and the substrate can be further improved.
  • limiting especially A hindered amine type thing can be used suitably especially.
  • hindered amine light stabilizers include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1 , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2, 2,6,6-tetramethyl-4-piperidyl) imino ⁇ ], N, N′-bis (3-aminopropyl) ethylenediamine ⁇ 2,4-bis [N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2,2,6,6-pentame Til-4-piperid
  • the light stabilizer is added in an amount of 0.1 to 7 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the crosslinkable silyl group-containing resin (A). Part.
  • the ultraviolet absorber may be added to the curable composition according to this embodiment.
  • the ultraviolet absorber has a function of absorbing ultraviolet rays and is effective in improving the weather resistance of the resin or imparting thermal stability.
  • an ultraviolet absorber it can use without a restriction
  • benzotriazole series examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy- 5′-octylphenyl) -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5′-di-tert-amylphenyl) benzotriazole, 2- ⁇ 2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, ”-Tetrahydrophthalimidomethyl) -5
  • Examples of the salicylic acid type include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.
  • the benzophenone series includes 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4- Examples thereof include methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and bis (2-methoxy-4-hydroxy-5-benzophenone) methane.
  • cyanoacrylates examples include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.
  • Triazines include 2- ⁇ 4 ′, 6′-bis (2 ′′, 4 ′′ -dimethylphenyl) -1 ′, 3 ′, 5′-triazine-2′-yl ⁇ -5- (octyloxy) phenol 2- (4 ′, 6′-diphenyl-1 ′, 3 ′, 5′-triazin-2′-yl) -5- (hexyloxy) phenol.
  • the addition amount of the ultraviolet absorber is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, more preferably 0.5 to 2 parts per 100 parts by mass of the crosslinkable silyl group-containing resin (A). Part by mass.
  • Coupling agent A coupling agent may be added to the curable composition according to this embodiment.
  • the coupling agent is effective for improving the adhesion between the curable composition and the inorganic substrate (target to be bonded or sealed).
  • the coupling agent is effective when an organic tin compound is used as the curing catalyst.
  • Examples of coupling agents include aminosilane-based cups such as aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2 (aminoethyl) aminopropyl trimethoxysilane.
  • epoxy silane such as glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane Coupling agents; mercaptosilane coupling agents such as mercatopropyltrimethoxysilane and mercatopropyltriethoxysilane; methyltrimethoxysilane, octadecyltrime Silane coupling agents such as xyloxysilane, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane; hexamethyldisilazane, hexaphenyldisilazane, dimethyl
  • Filler A filler may be added to the curable composition according to this embodiment.
  • the filler can be added for the purpose of high workability or strength reinforcement of the cured product of the curable composition.
  • the filler include inorganic oxides such as silica, titanium oxide, alumina, and zirconia, carbonates such as calcium carbonate and magnesium carbonate, and barium sulfate.
  • the filler include particles, plates, and fibers. it can. In particular, silica or calcium carbonate having a small particle size and good compatibility with the curable composition is preferable.
  • the addition amount of the filler is 2 to 99% by mass with respect to the total mass of the curable composition including the filler.
  • Plasticizer may be added to the curable resin composition according to this embodiment.
  • a plasticizer imparts flexibility to the material and helps to mix and disperse the formulation.
  • the plasticizer include phthalate esters such as dioctyl phthalate and diisononyl phthalate, adipate esters such as dioctyl adipate and diisononyl adipate, trimellitic acid ester, and pyromellitic acid citrate ester.
  • the addition amount of the plasticizer is 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 100 parts by mass of the crosslinkable silyl group-containing resin (A).
  • the curable composition according to this embodiment includes a crosslinkable silyl group-containing resin (A), a curing catalyst (B), a metal alkoxide-modified polysiloxane (C), and the like under an inert gas atmosphere such as nitrogen. Accordingly, it can be obtained by mixing other additive (D). Since oxygen and moisture contribute to the curing of the curable composition, it is preferably eliminated as much as possible in the mixing step. However, the complete elimination of oxygen and moisture is not an essential requirement. Basically, there is no major limitation in the order of mixing the above components, but before mixing the curing catalyst, the crosslinkable silyl group-containing resin, the metal alkoxide-modified polysiloxane, and other additives as required are evenly mixed.
  • the curing catalyst is composed of a plurality of types, if the components of the curing catalyst are brought into contact with each other, there is a risk of degrading the quality of the curing catalyst. It is preferable to mix with a functional silyl group-containing resin and to mix another component of the curing catalyst therein.
  • a functional silyl group-containing resin For example, 1- (o-tolyl) biguanide belonging to a guanidine compound tends to be unstable when mixed with a titanium chelate.
  • a curable composition by mixing the crosslinkable silyl group-containing resin in the order of metal alkoxide-modified polysiloxane, other additives, and a curing catalyst.
  • the curing catalyst is composed of a plurality of components, it is preferably prepared in advance prior to mixing with the crosslinkable silyl group-containing resin.
  • the curing catalyst is a combination of a titanium chelate and a guanidine compound (B1)
  • a titanium alkoxide titanium isopropoxide, etc.
  • a bidentate chelating agent ethyl acetoacetate, etc.
  • a titanium chelate is formed, and a guanidine compound (1,1,3,3-tetramethylguanidine or the like) is mixed therein. Since heat is generated during the production of the titanium chelate, it is preferable to mix the titanium alkoxide and the bidentate chelating agent while cooling. In addition, when it cools below the freezing point of a titanium alkoxide, a titanium alkoxide will solidify and it will be in a state which cannot be mixed, Therefore It is preferable to cool, keeping a temperature higher than the said freezing point.
  • the manufacturing method 1 of the curable composition includes a first mixing step of mixing the crosslinkable silyl group-containing resin (A) and the metal alkoxide-modified polysiloxane (C), A second mixing step in which the mixture obtained in the first mixing step is mixed with a curing catalyst (B: containing a combination of a titanium chelate and a guanidine compound (B1) or an organic tin compound (B2));
  • the production method 2 of the curable composition includes a third mixing step of mixing the crosslinkable silyl group-containing resin (A) and the guanidine compound, A fourth mixing step of mixing the metal alkoxide-modified polysiloxane (C) with the mixture obtained in the third mixing step; A fifth mixing step of mixing the titanium chelate with the mixture obtained in the fourth mixing step.
  • the curable composition production method 3 includes a sixth mixing step of mixing the crosslinkable silyl group-containing resin (A) and the metal alkoxide-modified polysiloxane (C), A seventh mixing step of mixing a guanidine compound with the mixture obtained in the sixth mixing step; And an eighth mixing step of mixing the titanium chelate with the mixture obtained in the seventh mixing step.
  • the step of mixing other additives (D) such as a light stabilizer, ultraviolet absorber, filler or coupling agent is performed before the step of mixing the curing catalyst (B) or the step of mixing the titanium chelate. Good to do.
  • the cured body according to this embodiment is obtained by curing any of the curable compositions described above.
  • the curable composition is cured by allowing the composition to exist at a predetermined location in the atmosphere at room temperature and leaving it for a predetermined time.
  • a more specific curing method is not particularly limited.
  • the temperature is 15 to 45 ° C., preferably 20 to 30 ° C. (room temperature: 23 ° C. is more preferable), 30 to 70% RH, preferably 40 to 60%. This is a method of standing in an environment of RH humidity.
  • the “predetermined time” is preferably a short time, but almost sure curing is achieved in 24 hours or more, and further in 168 hours.
  • the adhesive strength means an initial (about one day later) or later (about seven days later) adhesive strength. This is because, depending on the product and the form of use, it may be different in cases such as when it is desirable to develop adhesive strength in the initial stage, while it is desirable to develop adhesive strength at a relatively late stage.
  • ethyl acetoacetate manufactured by Kanto Chemical Co., Inc., hereinafter abbreviated as “EAcAc” was used.
  • EAcAc ethyl acetoacetate
  • C. Guanidine compounds
  • 1- (o-tolyl) biguanide Noxeller BG manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., hereinafter abbreviated as “BG”) and 1,1,3,3-tetramethylguanidine (Tokyo Chemical Industry)
  • BG Ouchi Shinsei Chemical Industry Co., Ltd., hereinafter abbreviated as “BG”
  • TMG 1,1,3,3-tetramethylguanidine
  • Organotin Compound Dibutyltin dilaurate manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter abbreviated as “DBTDL” was used as the organotin compound.
  • DBTDL Organotin Compound Dibutyltin dilaurate
  • Table 1 shows materials used for the production of alkoxysilane terminal-modified polysiloxane, which is an example of metal alkoxide-modified polysiloxane.
  • organopolysiloxanes As organopolysiloxanes, two types of polydimethylsiloxane (Momentive, product numbers: YF3800 and YF3057, hereinafter collectively referred to as “PDMS”) and one type of polydiphenyldimethylsiloxane (Momentive) , Product number: YF3804, hereinafter abbreviated as “PDPDMS”).
  • TMOS tetramethoxysilane
  • ES40 and ES45 ethyl silicate
  • Light stabilizer and ultraviolet absorber As the light stabilizer and ultraviolet absorber, hindered amine (Johoku Chemical Co., Ltd., product number: JF-90) and benzotriazole (Adeka Co., Ltd., product number: LA-36, respectively) ) was used.
  • G. Coupling agent Aminosilane manufactured by Tokyo Chemical Industry Co., Ltd., 3-aminopropyltrimethoxysilane was used as a coupling agent.
  • Preparation Example 2 Titanium chelate-TMG system TMG was placed in a screw tube bottle containing titanium chelate so that titanium chelate and TMG were equimolar, and stirred for 30 minutes using a magnetic stirrer.
  • Table 2 shows the prepared alkoxysilane terminal-modified polysiloxanes.
  • FIG. 1 schematically shows a terminal modification pattern of an assumed alkoxysilane terminal-modified polysiloxane.
  • ES45-3800 (1: 1)
  • ES product number: ES45
  • PDMS product number: YF3800
  • TTE titanium tetraethoxide
  • MA DL-malic acid diethyl ester
  • the above mixed liquid of TTE and MA was prepared by putting TTE and MA in the same mole in a screw tube bottle and stirring at 25 ° C. for 30 minutes (see Example 1 of WO2010 / 143357).
  • the mixed solution of TTE and MA has an effect of promoting the modification reaction of alkoxylane to organopolysiloxane.
  • Preparation Example a 0.0165 mol of the mixed solution of TTE and MA used in Preparation Example a was added to 1 mol of the mixed solution of TMOS and PDPDMS, and the mixture was stirred at room temperature for 24 hours while being sealed using a magnetic stirrer. .
  • the assumed form of the alkoxysilane terminal-modified polysiloxane of Preparation Example c is pattern (3) in FIG. (Preparation Example d) ... ES40-3057 (1: 1)
  • the assumed form of the alkoxysilane terminal-modified polysiloxane of Preparation Example d is the pattern (1) in FIG. (Preparation Example e) ES45 polymerized product-3800 (1: 1) In the same manner as in Preparation Example a, except that the heat polymerization of ES45 was advanced to prepare a product with Mn increased from 750 to 1300 (referred to as “ES45 polymerized product”) and the ES45 polymerized product was mixed with PDMS. Prepared.
  • the assumed form of the alkoxysilane terminal-modified polysiloxane of Preparation Example e is the pattern (4) in FIG. (Preparation Example f) ...
  • ES45 polymerized product-3800 (2: 1)
  • the assumed form of the alkoxysilane terminal-modified polysiloxane of Preparation Example f is the pattern (5) in FIG. (Preparation Example g) ...
  • the assumed form of the alkoxysilane terminal-modified polysiloxane of Preparation Example g is the pattern (6) in FIG.
  • Example 2 A curable composition was prepared under the same conditions as in Example 1 except that BG was increased to 0.4725 g (BG was 3 times the mole of titanium chelate).
  • Example 3 A curable composition was produced under the same conditions as in Example 1 except that the alkoxysilane terminal-modified polysiloxane of Preparation Example b was used instead of Preparation Example a (equal moles of titanium chelate and BG).
  • Example 4 14.25 g of silyl-terminated polyether (EST280) and 0.75 g of alkoxysilane-end-modified polysiloxane of Preparation Example c were placed in an ointment container and stirred for 1 minute using a rotation / revolution mixer. Next, 0.3 g of hindered amine (JF-90) as a light stabilizer and 0.15 g of benzotriazole (LA-36) as an ultraviolet absorber were added and further stirred for 1 minute. Next, 0.5475 g of a titanium chelate-TMG curing catalyst was added, and stirring for 3 minutes and defoaming treatment for 1 minute were performed to obtain a liquid curable composition (equal moles of titanium chelate and TMG).
  • JF-90 hindered amine
  • LA-36 benzotriazole
  • Example 5 A curable composition was prepared under the same conditions as in Example 1 except that the alkoxysilane terminal-modified polysiloxane of Preparation Example c was used instead of Preparation Example a (equal moles of titanium chelate and BG).
  • Example 6 A curable composition was prepared under the same conditions as in Example 1 except that the silyl-terminated polyether (EST280) was reduced to 12 g and 3 g of the alkoxysilane-end-modified polysiloxane of Preparation Example d was added instead of Preparation Example a (Titanium). Chelate and BG are equimolar).
  • Example 7 14.25 g of silyl-terminated polyether (EST280) and 0.75 g of the alkoxysilane-end-modified polysiloxane of Preparation Example a were placed in an ointment container and stirred for 1 minute using a rotation / revolution mixer. A curable composition was prepared under the same conditions as in Example 1 except that 0.15 g of DBTDL (referred to as Sn1) and 0.15 g of aminosilane were added in place of the curing catalyst of Example 1.
  • Sn1 DBTDL
  • aminosilane aminosilane
  • A2017S aluminum plate
  • Tables 3 and 4 show the preparation conditions of various cured compositions and the evaluation results of various cured bodies obtained by curing them.
  • FIG. 2 shows the adhesive strength (after 1 day and after 7 days) of Example 1 and Comparative Example 3 in comparison.
  • FIG. 3 shows a comparison of mechanical properties (elastic modulus, tensile fracture strength, elongation) of Example 1 and Comparative Example 3.
  • FIG. 4 shows a comparison of the adhesive strength (after 1 day and after 7 days) of Example 1, Example 2 and Comparative Example 1.
  • FIG. 5 shows the mechanical properties (elastic modulus, tensile fracture strength, elongation) of Example 1, Example 2 and Comparative Example 1 in comparison.
  • Example 7 shows the mechanical properties (elastic modulus, tensile fracture strength, elongation) of Example 7 and Comparative Example 6 in comparison. 2, 4 and 6, the adhesive strength (1d) after 1 day shows a left bar graph, and the adhesive strength (1w) after 7 days shows a right bar graph.
  • Example 1 to 4 and Example 6 both the adhesive strengths after 1 day and 7 days were high, and the effect of enhancing the adhesive strength was great.
  • Example 5 compared with Comparative Example 3, it only contributes to the improvement of the adhesive strength after 7 days. Therefore, it was found that the contributions of both end-modified polysiloxanes differ depending on the type of guanidine compound.
  • FIGS. 2 and 3 when the adhesive strength and mechanical properties of Example 1 and Comparative Example 3 having a difference in the presence or absence of the modified polymer are compared, the addition of the modified polymer results in an increase in the modulus of elasticity and tensile fracture strength. An improvement is observed, and this is considered to affect the improvement of the adhesive strength.
  • Example 7 Furthermore, from the comparison between Example 7 and Comparative Example 6 using a tin-based catalyst, it was found that the presence of the modified polymer contributed to the improvement of the adhesive strength after 1 day and after 7 days. Further, in all of the examples, the skinning time exceeds 30 minutes, and the work life from the application process to the application process can be increased, so that improvement in workability can be expected.
  • Example 1 From a comparison between Example 1 and Example 2, it was found that the adhesive strength increased when the guanidine compound was increased by a factor of 3 by mass ratio. From the comparison between Example 1 and Example 3, it is better to construct both end-modified polysiloxanes by doubling the molar ratio of the alkoxysilane for terminal modification in terms of molar ratio, and to improve the adhesive strength, especially the adhesive strength after one day. I found out that The same applies to Example 4 in which the type of both end-modified polysiloxane was changed to TMOS-PDPDMS, and Example 6 in which the type of terminal-modified polysiloxane was changed to ES40-PDPDMS.
  • Example 1 As shown in FIG. 4 and FIG. 5, when the adhesive strength and mechanical properties of Example 1, Example 2 and Comparative Example 1 are compared, there is not necessarily a correlation between the improvement of the adhesive strength and the elastic modulus or tensile fracture strength. Since it is not recognized, it is considered that the adhesion at the interface between the cured body and the aluminum plate is involved in improving the adhesive strength in addition to the strength of the cured body itself.
  • Example 7 and Comparative Example 6 when the adhesive strength and mechanical properties of Example 7 and Comparative Example 6 were compared, a correlation between the improvement of the adhesive strength and the elastic modulus or tensile fracture strength was observed. From this, it is considered that when a tin-based catalyst is used, the strength of the cured body itself is involved in improving the adhesive strength.
  • Evaluation method> The evaluation is the previous ⁇ 5. Evaluation method> and the same method.
  • Table 5 shows the preparation conditions of the various cured compositions of Examples 8 and 9 and the evaluation results of the various cured products obtained by curing them. For comparison, the previous Example 3 is also shown in Table 5.
  • the denaturation rate (%) was calculated as follows.
  • ES-3804 will be described using an alkoxysilane terminal-modified polysiloxane.
  • the ES amount after the modified PDPDMS synthesis process is estimated by GPC with respect to the ES amount before the modification treatment.
  • FIG. 8 shows a GPC curve (8A) before denaturation treatment and a curve (8B) before and after waveform separation of the ES peak intensity.
  • the denaturation rate of ES modified PDPDMS is obtained from the ES consumption. Specifically, the modification rate (%) was obtained from both the following formulas.
  • Example 11 The alkoxysilane terminal-modified polysiloxane of Preparation Example g was heated at 130 ° C. for 6 hours to prepare an alkoxysilane terminal-modified polysiloxane having a modification rate of 97%.
  • a liquid curable composition was obtained under the same conditions as in Example 10, except that 13.5 g of silyl-terminated polyether (EST280) was mixed.
  • the modification rate was calculated by the same method as in Example 10.
  • Example 12 The same as Example 11 except that after the treatment for reducing the low-molecular components from the alkoxysilane terminal-modified polysiloxane having a modification rate of 97%, 1.5 g thereof was mixed with 13.5 g of silyl-terminated polyether (EST280).
  • ES45: PDPDMS 2: 1 (molar ratio)
  • ES45 and PDPDMS were prepared, except that 1.5 g of ES45 + PDPDMS was taken in total, and this was mixed with 13.5 g of silyl-terminated polyether (EST280).
  • a liquid curable composition was obtained under the same conditions as in Example 10. In Comparative Example 7, the modification rate was considered to be zero.
  • Evaluation method> The evaluation is the previous ⁇ 5. Evaluation method> and the same method.
  • FIG. 9 is a chart (9A) showing a change in GPC of an alkoxysilane-end-modified polysiloxane (ES45-PDPDMS) having a modification rate of 91%, a modification rate of 93%, and a modification rate of 97% before the modification treatment and up to a modification rate of 97%.
  • ES45-PDPDMS alkoxysilane-end-modified polysiloxane
  • a chart (9B) showing a comparison of the GPCs of the low molecular component reduction treatment after the denaturation treatment and the low molecular component reduction treatment is shown.
  • the present invention can be used for, for example, an adhesive and a sealing material.

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Abstract

Le problème abordé par la présente invention est de pourvoir à une composition durcissable à un composant ayant d'excellentes propriétés de durcissement, et un corps durci à base de ladite composition. La solution selon l'invention porte sur : une composition durcissable comprenant (A) une résine réticulable contenant un groupe silyle, (B) un catalyseur de durcissement contenant (B1) une combinaison constituée d'un chélateur de titane et d'un composé de guanidine ou (B2) un composé d'étain organique, (C) un polysiloxane modifié par un alcoxyde métallique ; et le corps durci formé par durcissement de la composition.
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CN115181273A (zh) * 2022-08-25 2022-10-14 江西天永诚高分子材料有限公司 一种脱醇型室温硫化硅橡胶及其制备方法

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