WO2022131116A1 - Catalyseur de durcissement utilisé pour durcir un polymère, composition durcissable à l'humidité et procédé de production d'un produit durci - Google Patents

Catalyseur de durcissement utilisé pour durcir un polymère, composition durcissable à l'humidité et procédé de production d'un produit durci Download PDF

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WO2022131116A1
WO2022131116A1 PCT/JP2021/045285 JP2021045285W WO2022131116A1 WO 2022131116 A1 WO2022131116 A1 WO 2022131116A1 JP 2021045285 W JP2021045285 W JP 2021045285W WO 2022131116 A1 WO2022131116 A1 WO 2022131116A1
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group
curing catalyst
polymer
curing
organic group
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PCT/JP2021/045285
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Japanese (ja)
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裕士 今田
侑哉 中川
和則 難波
春香 吉山
奈那恵 菊井
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日東化成株式会社
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    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • 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

Definitions

  • the present invention relates to a curing catalyst used for curing a polymer, a moisture-curable composition, and a method for producing a cured product.
  • the one-component moisture-curable rubber composition generally has a high curing rate, and it is not necessary to weigh and mix various additives such as a base polymer, a cross-linking agent, and a catalyst before use, so that the one-component type is a two-component type. It is superior in terms of workability.
  • silicone-based rubbers silicone-based rubbers, modified silicone-based rubbers, urethane-based rubbers, polysulfide-based rubbers, and the like are known.
  • An organopolysiloxane composition is widely used as a one-component moisture-curable rubber composition of a silicone-based rubber, and is cured at room temperature to form a rubber elastic body.
  • the polymer compound of siloxane whose main chain is a -Si-O- bond obtained by cross-linking and polymerizing organosiloxane is excellent in properties such as water repellency, heat resistance, weather resistance, cold resistance, and electrical insulation. It is widely used in the fields of civil engineering, electricity, electronics, automobile industry, etc.
  • a one-component moisture-curable rubber composition of modified silicone-based rubber there is a composition containing a polymer having a crosslinkable reactive hydrolyzable silicon functional group having a polyether as a main chain.
  • the curable composition of this polymer has better storage stability, weather resistance, foaming resistance and discoloration resistance than those of polyurethane-based rubber, and is superior in curability to surroundings as compared with polysulfide-based ones. It is less contaminated and non-toxic.
  • the reaction mechanism in the process of the silicone-based rubber and the modified silicone-based rubber becoming a cured product is said to be due to the condensation reaction or addition reaction of the reactive hydrolyzable silicon-containing group in the coexistence of water, and the polymerization proceeds. It is believed that a cured polymer with a three-dimensional network structure is formed. Curing catalysts are used to accelerate curing in this reaction (Patent Documents 1 to 4).
  • tin carboxylate compounds As a curing catalyst for a curing composition of a silicone-based rubber having a reactive hydrolyzable silicon-containing group and a modified silicone-based rubber, tin carboxylate compounds, alkyl tin salt compounds and the like have been conventionally used, but endocrine disruption is disrupted. Since there is concern about the effect on the living body as a substance, a combined catalyst of a carboxylic acid and an amine (Patent Document 1) has been proposed as a moisture-curable composition that does not use such a substance, but it is sufficiently cured at the time of construction. There is a problem that speed cannot be obtained.
  • Patent Document 2 and Patent Document 3 it is proposed to use a titanium acid ester compound such as diisopropoxytitanium bis (alkylacetoacetonate) as a catalyst, but it is contained in additives and fillers in the composition. It is easily decomposed by the moisture, and the curing speed varies depending on the humidity at the time of construction, so that there is a problem that a stable cured product cannot be obtained.
  • a titanium acid ester compound such as diisopropoxytitanium bis (alkylacetoacetonate)
  • Patent Document 4 proposes the use of a titanium tetracarboxylate compound as a catalyst, but there is a problem that practical satisfaction with respect to the curing rate cannot be obtained.
  • an object of the present invention is to provide a curing catalyst having high safety and a practical curing rate.
  • the curing catalyst [B] used for curing the polymer [A] having a reactive hydrolyzable silicon-containing group wherein the curing catalyst [B] contains phosphazene [B1].
  • the phosphazen [B1] a curing catalyst [B] represented by the chemical formula (1) is provided.
  • the present inventor has found that the curing rate of the polymer [A] is significantly increased when the curing catalyst [B] containing phosphazene [B1] is used, and the present invention is completed. Arrived at. Since this catalyst does not contain tin, it is highly safe. In addition, it can be manufactured at low cost.
  • the curing catalyst [B] of the present invention is used for curing a polymer [A] having a reactive hydrolyzable silicon-containing group.
  • the polymer [A] is preferably liquid at room temperature.
  • the polymer [A] has at least one reactive hydrolyzable silicon-containing group per molecule at the molecular end or side chain.
  • the reactive hydrolyzable silicon-containing group may be present at the terminal of the polymer [A] molecule, at the side chain, or at both the terminal and the side chain.
  • the number of reactive hydrolyzable silicon-containing groups may be at least one per molecule of the polymer [A], but the number is 1.5 or more per molecule on average in terms of curing rate and cured physical characteristics. Is preferable.
  • a known method can be adopted as a method for binding the reactive hydrolyzable silicon-containing group to the backbone polymer.
  • a reactive hydrolyzable silicon-containing group is a group having a silicon atom bonded to a hydrolyzable group (eg, halogen, alkoxy, alkenyloxy, asyloxy, amino, aminooxy, oxime, amide) or a reactive group consisting of a hydroxyl group. It has the property of causing a condensation reaction by using a catalyst or the like as needed in the presence of moisture or a cross-linking agent. Specific examples thereof include a halide silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximsilyl group, and an amidosilyl group.
  • the number of reactive hydrolyzable groups bonded to one silicon atom is selected from the range of 1 to 3. Further, the reactive hydrolyzable group bonded to one silicon atom may be one kind or a plurality of kinds. Further, the reactive hydrolyzable group and the non-reactive hydrolyzable group may be bonded to one silicon atom, or the hydrolyzable group and the hydroxyl group may be bonded to one silicon atom.
  • the reactive hydrolyzable silicon-containing group an alkoxysilyl group (including a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group) is particularly preferable because it is easy to handle.
  • the trialkoxysilyl group is preferable because it has high activity and good curability can be obtained, and the obtained cured product is excellent in restorability, durability and creep resistance.
  • the dialkoxysilyl group and the monoalkoxysilyl group are preferable because they have excellent storage stability and the obtained cured product has high elongation and high strength.
  • the polymer [A] used in the present invention has a carbon atom as the main chain, for example, an alkylene oxide polymer, a polyester polymer, an ether / ester block copolymer, a polymer of an ethylenically unsaturated compound, or a diene system.
  • a carbon atom for example, an alkylene oxide polymer, a polyester polymer, an ether / ester block copolymer, a polymer of an ethylenically unsaturated compound, or a diene system.
  • examples include polymers of compounds.
  • the alkylene oxide polymer [CH 2 CH 2 O] n [CH (CH 3 ) CH 2 O] n [CH (C 2 H 5 ) CH 2 O] n [CH 2 CH 2 CH 2 CH 2 O] n
  • n is the same or different integer of 2 or more.
  • These alkylene oxide polymers may be used alone or in combination of two or more. Further, a copolymer containing two or more of the above repeating units can also be used.
  • polyester polymer examples include carboxylic acids such as acetic acid, propionic acid, maleic acid, phthalic acid, citric acid, pyruvate, and lactic acid and their anhydrides, and their intramolecular and / or intermolecular esters and their substitutions. Examples are those having as a repeating unit.
  • ether / ester block copolymer examples include those having both the repeating unit used for the above-mentioned alkylene oxide polymer and the repeating unit used for the above-mentioned polyester polymer as the repeating unit.
  • the polymers of the ethylenically unsaturated compound and the diene compound include ethylene, propylene, acrylic acid ester, methacrylic acid ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene and other homopolymers, or Examples thereof include these two or more kinds of copolymers. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid.
  • Ester copolymer polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylic acid ester, polymethacrylic acid Examples include esters. These may be used alone or in combination of two or more.
  • an organic polymer having a polar group such as a nitrogen-containing characteristic group in the molecule can also be used.
  • a nitrogen-containing characteristic group include (thio) urethane group, allophanate group, other N-substituted urethane group, N-substituted allophanate group and other (thio) urethane group-derived linking group, (thio) urea group, and the like.
  • Biling group derived from (thio) urea group such as biuret group, other N-substituted urea group, N, N'-substituted urea group, N-substituted biuret group, N, N'-substituted biuret group, amide group
  • Examples include, but are limited to, a binding group derived from an amide group such as an N-substituted amide group, a nitrogen-containing characteristic group represented by a binding group derived from an imino group, a (thio) ester group, a (thio) ether group, and the like. Not done.
  • a nitrogen-containing characteristic group is preferable because of its high curability, and a (thio) urethane group-derived binding group and a (thio) urea-derived binding group are more preferable because of its ease of synthesis. Further, only one nitrogen-containing characteristic group may be contained in the polymer [A], and one or more nitrogen-containing characteristic groups may be further contained.
  • the notations of "(thio)" and "N-substitution" are the same as above.
  • the toughness of the cured product is improved, and the curability and the adhesive strength are enhanced.
  • the crosslinkable silicon group is linked to the main chain via a polar group such as a nitrogen-containing characteristic group, the curability is further enhanced.
  • the polar groups of the nitrogen-containing characteristic groups are strongly attracted to each other by an interaction such as a hydrogen bond. It is considered that the polar groups of the nitrogen-containing characteristic groups are strongly attracted to each other, so that the molecules of the curable resin are also strongly bound to each other (domain formation), thereby exhibiting toughness in the cured product.
  • the crosslinkable silicon groups are also close to each other when forming a domain between the nitrogen-containing characteristic groups.
  • the contact probability between the crosslinkable silicon groups is also improved, and further, the condensation reactivity between the crosslinkable silicon groups is improved by catalytic curing by the polar group in the nitrogen-containing characteristic group.
  • Such a polymer [A] can be produced by a known method such as the method described in Japanese Patent Publication No. 61-18569, or is commercially available.
  • Commercially available products include, for example, Kaneka MS Polymer series (MS Polymer S203, MS Polymer S303, MS Polymer S903, MS Polymer S911, MS Polymer SAX520, etc.) and Cyril Series (Cyril Polymer SAT200, Cyril) manufactured by Kaneka Corporation.
  • Polymer MA430, Cyril Polymer MAX447, etc.), MA series, SA series, OR series; ES series (ES-GX3440ST, etc.) manufactured by Asahi Glass Co., Ltd., ESGX series, etc. are exemplified.
  • the number average molecular weight of the polymer [A] used in the present invention is not particularly limited, but an excessively high polymer has a high viscosity and is difficult to use in the case of a curable composition, so it is 30,000 or less. Is desirable.
  • Such a polymer can be produced by a known method, but a commercially available product such as the above-mentioned Kaneka MS polymer manufactured by Kaneka Corporation may be used.
  • the curing catalyst [B] contains phosphazene [B1].
  • Phosphazene [B1] is expressed by the following formula.
  • X is a monovalent organic group having 1 to 18 carbon atoms
  • Y is a monovalent organic group that is the same as or different from each other, or is a divalent organic composed of two Ys linked to each other. It is the basis.
  • the number of carbon atoms of the monovalent organic group constituting X is preferably 1 to 10, more preferably 1 to 4, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 It is 10, 11, 12, 13, 14, 15, 16, 17, and 18, and may be within the range between any two of the numerical values exemplified here.
  • This organic group may be composed only of carbon and hydrogen, or may contain other atoms (for example, at least one of an oxygen atom and a nitrogen atom).
  • This organic group is, for example, an aromatic or aliphatic hydrocarbon group which may have a substituent, and an aliphatic hydrocarbon group is preferable.
  • an alkyl group is preferable.
  • the monovalent organic group constituting Y has, for example, 1 to 18, preferably 1 to 10, more preferably 2 to 4, and specifically, for example, 1, 2, 3, 4, 5, and so on. It is 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and may be within the range between any two of the numerical values exemplified here.
  • the organic group preferably contains carbon and hydrogen.
  • This organic group preferably contains a nitrogen atom, and the atom directly bonded to the phosphorus atom of the chemical formula (1) is preferably a nitrogen atom.
  • the number of nitrogen atoms contained in this organic group is, for example, 1, 2, 3, or 4.
  • This organic group may or may not contain a phosphorus atom.
  • the number of phosphorus atoms contained in this organic group is preferably 0 or 1.
  • the phosphorus atom is preferably bonded to the nitrogen atom.
  • This organic group may contain other atoms (eg, at least one of an oxygen atom, a sulfur atom and a halogen atom).
  • the number of phosphorus atoms contained in phosphazene [B1] is, for example, 1, 2, 3, or 4.
  • the number of nitrogen atoms contained in phosphazene [B1] is, for example, 1 to 13, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and so on. It is 13, and may be within the range between any two of the numerical values exemplified here.
  • the number of double bonds of nitrogen atom and phosphorus atom contained in phosphazene [B1] is, for example, 1, 2, 3, or 4.
  • At least one of Y is preferably represented by the chemical formula (2) or the chemical formula (3).
  • R 1 is a monovalent organic group or a divalent organic group composed of two R 1s linked to each other.
  • the description of the monovalent organic group constituting R 1 is the same as the description of the monovalent organic group constituting X.
  • the number of carbon atoms of the divalent organic group composed of two R1s linked to each other is, for example, 1 to 18, preferably 1 to 10, more preferably 2 to 4, and specifically, for example, 1. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and within the range between any two of the numerical values exemplified here. May be.
  • a cyclic structure is formed by this organic group and the nitrogen atom to which this organic group is bonded.
  • This organic group may be composed only of carbon and hydrogen, or may contain other atoms (for example, at least one of an oxygen atom and a nitrogen atom).
  • This organic group is, for example, an aromatic or aliphatic hydrocarbon group which may have a substituent, and an aliphatic hydrocarbon group is preferable.
  • an alkylene group is preferable.
  • the number of carbon atoms of the divalent organic group formed by connecting two Ys in the chemical formula (1) to each other is, for example, 1 to 18, preferably 1 to 10, and specifically, for example, 1, 2, and so on. 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and are within the range between any two of the numerical values exemplified here. You may.
  • a cyclic structure is formed by this organic group and the phosphorus atom to which this organic group is bonded.
  • the organic group preferably contains carbon and hydrogen.
  • This organic group preferably contains a nitrogen atom, and the atom directly bonded to the phosphorus atom of the chemical formula (1) is preferably a nitrogen atom.
  • the number of nitrogen atoms contained in this organic group is, for example, 2.
  • the organic group may contain other atoms (eg, at least one of an oxygen atom, a phosphorus atom, a sulfur atom and a halogen atom).
  • the divalent organic group formed by linking two Ys in the chemical formula (1) to each other is preferably represented by the chemical formula (4).
  • * is a bond
  • R 2 is a divalent organic group
  • R 3 is a monovalent organic group
  • two R 3s are linked to each other. It is a divalent organic group.
  • the divalent organic group constituting R 2 In the description of the divalent organic group constituting R 2 and the description of the divalent organic group in which two R 3s are linked to each other, the two R 1s in the chemical formula (2) are linked to each other. It is the same as the description of the composed divalent organic group.
  • the description of the monovalent organic group constituting R 3 is the same as the description of the monovalent organic group constituting X.
  • the Y in the chemical formula (1) is, for example, N, N'-dimethylamino group, N, N'-diethylamino group, N, N'-dipropylamino group, N, N'-diisopropyl.
  • the curing catalyst [B] may further contain a titanium compound [B2].
  • the titanium compound [B2] is a compound containing a titanium atom, and it is preferable that at least one of the ligands coordinated to the titanium atom is an alkoxy group.
  • the number of ligands is preferably 4.
  • the number of alkoxy groups contained in the ligand is, for example, 1, 2, 3, or 4.
  • the ligand may contain a group other than the alkoxy group, and examples of such a group include an alkyl group, a carboxyl group, a ⁇ -diketone group and the like.
  • the carbon number of these ligands is, for example, 1 to 18, preferably 1 to 10, more preferably 2 to 4, and specifically, for example, 1, 2, 3, 4, 5, 6, and so on. It is 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and may be within the range between any two of the numerical values exemplified here.
  • the titanium compound [B2] is preferably represented by the chemical formula (5). (R 4 -O) n Ti-A 4-n (5)
  • R4 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 4 (that is, 1, 2, 3, or 4), and A is. It is a ⁇ -diketone group.
  • the substituted or unsubstituted hydrocarbon group represented by R4 is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferable.
  • the aliphatic hydrocarbon group include saturated or unsaturated hydrocarbon groups.
  • As the saturated hydrocarbon group a linear or branched alkyl group is preferable.
  • the hydrocarbon group has 1 to 10 carbon atoms, preferably 1 to 6 and even more preferably 1 to 4. Specifically, the number of carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, and is within the range between any two of the numerical values exemplified here. May be good.
  • hydrocarbon group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl.
  • the ⁇ -diketone group represented by A includes 2,4-pentandione, 2,4-hexanedione, 2,4-pentadecandione, 2,2,6,6-tetramethyl-3,5-heptandione, 1 -Phenyl-1,3-butandione, 1-aryl-1,3-butandione such as 1- (4-methoxyphenyl) -1,3-butandione, 1,3-diphenyl-1,3-propanedione, 1, 1,3-Diaryl-1,3-propanedione such as 3-bis (2-pyridyl) -1,3-propanedione, 1,3-bis (4-methoxyphenyl) -1,3-propanedione, 3 -Diketones such as benzyl-2,4-pentandione, ketoesters such as methylacetate, ethylacetate, butylacetate, t-butylacetate, ethyl3
  • titanium compound [B2] examples include tetramethoxytitanium, trimethoxyethoxycititanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, and methoxytri.
  • the above titanium compound [B2] may be used alone or in combination of two or more.
  • the content ratio (B1 / B2) of the phosphazene [B1] and the titanium compound [B2] is in the range of 3/1 to 1/2 in terms of molar ratio, and is 3/1 from the viewpoint of obtaining good curability. ⁇ 1/1 is preferable, and 2/1 to 1/1 is more preferable.
  • the moisture-curable composition of the present invention contains the above-mentioned curing catalyst [B] and polymer [A], and may contain other additives described later, if necessary.
  • the moisture-curable composition of the present invention may be prepared by mixing the two under dry conditions, and the mixing form thereof is not particularly limited. Usually, it may be mixed in an atmosphere of about 15 to 30 ° C. and 60% RH or less.
  • the content of the curing catalyst [B] is 0.1 to 20 parts by weight, more particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer [A]. 3 to 8 parts by weight is preferable. If the content of the curing catalyst [B] is less than 0.1 parts by weight, the curing performance is insufficient, and if it exceeds 20 parts by weight, the restoration rate of the cured product after curing, physical properties such as weather resistance, and stability during storage. May get worse.
  • the content of the curing catalyst [B] is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, with respect to 100 parts by weight of the polymer [A]. It is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 parts by mass, and may be within the range between any two of the numerical values exemplified here.
  • the filler [C] may be further added to the moisture-curable composition of the present invention.
  • the filler include calcium carbonate, kaolin, talc, fumed silica, precipitated silica, silicic acid anhydride, hydrous silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, silasburn, glass fiber, asbestos, and the like. Examples thereof include glass filament, crushed quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, titanium dioxide and the like.
  • the filler may be used alone or in combination of two or more.
  • the addition of the filler improves the handling of the moisture-curable composition. It also works as a rubber reinforcing agent for cured products. The biggest merit is that the amount of resin used can be reduced by adding it as a bulking agent, so that the cost can be reduced.
  • calcium carbonate and titanium oxide are preferable from the viewpoint of maintaining excellent surface non-tack, 50% modulus, workability, weather resistance and the like of the curable composition after curing.
  • the ratio thereof is preferably 1 to 200 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the polymer [A]. Within the above range, the characteristics after curing are not impaired.
  • curable composition of the present invention other curing catalysts, curing accelerators, colorants, plasticizers, curing retarders, sagging inhibitors, antiaging agents, solvents and the like are usually added to curable compositions. Additives may be added.
  • curing catalysts examples include organic tin compounds such as dibutyltin dilaurate and dibutyltin bis (acetylacetonate), organic aluminum compounds such as aluminumtris (acetylacetonate) and aluminumtris (ethylacetoacetate), and zirconium tetra (acetyl).
  • organic tin compounds such as dibutyltin dilaurate and dibutyltin bis (acetylacetonate)
  • organic aluminum compounds such as aluminumtris (acetylacetonate) and aluminumtris (ethylacetoacetate)
  • zirconium tetra acetyl
  • organic zirconium compounds such as zirconite tetrabutyrate
  • metal curing catalysts such as 1-amino-2-ethylhexane, 3- (trimethoxysilyl) propylamine, N-2-aminoethyl-3-aminopropyl Trimethoxysilane, N, N, N', N'-tetramethyl-N''-[3- (trimethoxysilyl) propyl] guanidine, 1,5,7-triazabicyclo-[4,4,0]
  • Examples thereof include amine compounds such as deca-5-ene and 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine.
  • the curing accelerator for example, various known amino group-substituted alkoxysilane compounds or condensates thereof can be used. Specifically, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, ⁇ -aminobutyl (methyl) diethoxysilane, N, N-bis (tri). Examples thereof include methoxysilylpropyl) ethylenediamine and partial hydrolysis of these, which also have the effect of improving the adhesion to the substrate.
  • iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, etc. are used as the colorant.
  • plasticizer examples include phthalates such as dibutylphthalate, dioctylphthalate, and butylbenzylphthalate; fatty acid carboxylic acid esters such as dioctyl adipate, dioctyl succinate, diisodecyl succinate, and butyl oleate; penta.
  • Glycol esters such as erythritol esters; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; chlorinated paraffin and the like are used.
  • hydrogenated castor oil silicic acid anhydride, organic bentonite, colloidal silica, etc. are used as the anti-sauce agent.
  • adhesives such as phenol resins and epoxy resins, ultraviolet absorbers, radical chain inhibitors, peroxide decomposition agents, various antiaging agents and the like are used.
  • the curable composition of the present invention is sufficiently stable at room temperature and therefore has excellent storability, and when it comes into contact with moisture, the curing reaction spontaneously proceeds by the compounded curing catalyst [B].
  • the snap time (time until semi-gelation and loss of fluidity) and tack free time (time until surface tack disappears) are short, and workability is excellent.
  • the curable composition of the present invention can be used as a one-component sealing material. Specifically, it is suitably used for applications such as sealing materials for vehicles such as buildings, ships, and automobiles, adhesives, sealing agents, and sealing materials for waterproofing.
  • the catalyst compositions 1 to 4 and titanium acetate triisopropoxide were produced according to the following production examples.
  • the catalyst compositions 1 to 4 are curing catalysts composed of a mixture of phosphazene compound 1 and tetraisopropoxytitanium.
  • MS Polymer SAX520 Organic Polymer Containing a Cyril Group (manufactured by Kaneka Corporation)
  • MS Polymer S303 Cyril group-containing organic polymer (manufactured by Kaneka Corporation)
  • STP-E15 Cyril group-containing organic polymer GENIOSIL STP-E15 (manufactured by WACKER Chemical Corporation)
  • Tetraisopropoxytitanium Titanium acetate triisopropoxide manufactured by Tokyo Chemical Industry Co., Ltd .: Manufactured in Comparative Production Example 1.
  • Carlex 300 Calcium carbonate (manufactured by Maruo Calcium Co., Ltd.)
  • FR-41 Titanium oxide (manufactured by Furukawa Chemicals Co., Ltd.)
  • REOLOSIL PM-20 Fumed Silica (manufactured by Tokuyama Corporation)
  • DINP Plasticizer (manufactured by J-PLUS Co., Ltd.)
  • PPG1000 Plasticizer (manufactured by Kishida Chemical Co., Ltd.)
  • Disparon 6500 Anti-sauce agent (manufactured by Kusumoto Chemical Co., Ltd.)
  • Songsorb 3260P UV absorber (manufactured by SONGWON)
  • Sabostab UV70 Light stabilizer (manufactured by SONGWON)
  • Irganox245 Antioxidant (manufactured by BASF Japan Ltd.)
  • KBM-1003 Dehydrating agent (manufactured by Shinetsu Silicone Industry Co., Ltd.)
  • KBM-903 Adhesive enhancer (manufactured by Shinetsu Silicone Industry Co., Ltd.)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

L'objet de la présente invention est de fournir un catalyseur de durcissement qui est hautement stable et qui a une vitesse de durcissement pratique.　La présente invention concerne un catalyseur de durcissement [B] destiné à être utilisé pour durcir un polymère [A] comprenant un groupe contenant du silicium hydrolysable réactif, le catalyseur de durcissement [B] contenant un phosphazène [B1], et le phosphazène [B1] étant représenté par la formule chimique (1).
PCT/JP2021/045285 2020-12-15 2021-12-09 Catalyseur de durcissement utilisé pour durcir un polymère, composition durcissable à l'humidité et procédé de production d'un produit durci WO2022131116A1 (fr)

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JP2020207932A JP2022094833A (ja) 2020-12-15 2020-12-15 重合体の硬化に用いる硬化触媒、湿気硬化型組成物、硬化物の製造方法

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160724A (ja) * 1997-08-19 1999-03-05 Mitsui Chem Inc ケイ素基含有ポリアルキレンオキサイド重合体の製造方法及び湿気硬化性組成物
JP2012522117A (ja) * 2009-03-31 2012-09-20 ダウ コーニング コーポレーション 分岐オルガノポリシロキサン
WO2015052859A1 (fr) * 2013-10-10 2015-04-16 信越化学工業株式会社 Composition de résine durcissant à température ambiante
JP2015527436A (ja) * 2012-06-27 2015-09-17 スリーエム イノベイティブ プロパティズ カンパニー 水分硬化性ポリシロキサンコーティング組成物
JP2019194692A (ja) * 2018-04-27 2019-11-07 東京応化工業株式会社 感エネルギー性組成物、硬化物、及びパターン形成方法
JP2020169274A (ja) * 2019-04-03 2020-10-15 日立化成株式会社 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160724A (ja) * 1997-08-19 1999-03-05 Mitsui Chem Inc ケイ素基含有ポリアルキレンオキサイド重合体の製造方法及び湿気硬化性組成物
JP2012522117A (ja) * 2009-03-31 2012-09-20 ダウ コーニング コーポレーション 分岐オルガノポリシロキサン
JP2015527436A (ja) * 2012-06-27 2015-09-17 スリーエム イノベイティブ プロパティズ カンパニー 水分硬化性ポリシロキサンコーティング組成物
WO2015052859A1 (fr) * 2013-10-10 2015-04-16 信越化学工業株式会社 Composition de résine durcissant à température ambiante
JP2019194692A (ja) * 2018-04-27 2019-11-07 東京応化工業株式会社 感エネルギー性組成物、硬化物、及びパターン形成方法
JP2020169274A (ja) * 2019-04-03 2020-10-15 日立化成株式会社 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ

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