WO2023171425A1 - Mélange de polymères à base de polyoxyalkylène et composition durcissable - Google Patents

Mélange de polymères à base de polyoxyalkylène et composition durcissable Download PDF

Info

Publication number
WO2023171425A1
WO2023171425A1 PCT/JP2023/006849 JP2023006849W WO2023171425A1 WO 2023171425 A1 WO2023171425 A1 WO 2023171425A1 JP 2023006849 W JP2023006849 W JP 2023006849W WO 2023171425 A1 WO2023171425 A1 WO 2023171425A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polymer
polyoxyalkylene
hydrolyzable silyl
polyoxyalkylene polymer
Prior art date
Application number
PCT/JP2023/006849
Other languages
English (en)
Japanese (ja)
Inventor
翔大 神谷
丈尋 伊丹
Original Assignee
株式会社カネカ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社カネカ filed Critical 株式会社カネカ
Publication of WO2023171425A1 publication Critical patent/WO2023171425A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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 mixture of polyoxyalkylene polymers having a hydrolyzable silyl group, and a curable composition containing the mixture.
  • Polymers with hydrolyzable silyl groups are known as moisture-reactive polymers, and their curable compositions are used in many industrial products such as adhesives, sealants, coatings, paints, and adhesives. It is used in a wide range of fields.
  • such a curable composition is preferably one that develops adhesiveness and hardness in a short time and has excellent rising properties. Specifically, it is desirable to exhibit adhesive strength comparable to the final strength one day after construction.
  • methods are known that use polymers having trialkoxysilyl groups (see, for example, Patent Document 1). ).
  • Patent Document 2 provides a method of using a polymer having a dialkoxylyl group and a polymer having a trialkoxysilyl group in combination.
  • the above-mentioned method requires the use of a polymer having a trialkoxysilyl group, and the use of only a polymer having a dimethoxysilyl group was insufficient to increase adhesive strength. Further, even when used in combination with a trialkoxysilyl group, there is still room for improvement in the rise of adhesive strength.
  • the present invention provides a mixture of a hydrolyzable silyl group-containing polyoxyalkylene polymer with improved adhesive strength rise, a curable composition containing the same, and a method for curing the curable composition.
  • the purpose is to provide a cured product.
  • the present inventors have created a mixture of hydrolyzable silyl group-containing polyoxyalkylene polymers having a specific molecular weight, a specific main chain structure, and a specific hydrolyzable silyl group introduction rate.
  • the inventors have found that the adhesive strength increases faster and exhibits better curability than when these polymers are used alone, leading to the completion of the present invention.
  • the present invention has a main chain structure of polyoxyalkylene and a terminal structure bonded to the terminal of the main chain structure, and the terminal structure has a hydrolyzable silyl group, a terminal olefin group, and/or an internal A mixture of a polyoxyalkylene polymer (A) and a polyoxyalkylene polymer (B) having an olefin group,
  • the polyoxyalkylene polymer (A) has a linear main chain structure and has one terminal structure in one molecule,
  • the number of moles of hydrolyzable silyl group/(total number of moles of hydrolyzable silyl group, terminal olefin group, and internal olefin group) is 0.50 or more and less than 1.00,
  • the number average molecular weight is 1,000 or more and 8,000 or less
  • the polyoxyalkylene polymer (B) has a branched main chain structure, The number of moles of the hydrolyzable silyl group/(the total number of mo
  • a mixture of a hydrolyzable silyl group-containing polyoxyalkylene polymer with improved rise in adhesive strength, a curable composition containing the same, and a cured product obtained by curing the curable composition can be provided.
  • the mixture of hydrolyzable silyl group-containing polyoxyalkylene polymers according to the present embodiment includes a polyoxyalkylene polymer (A) and a polyoxyalkylene polymer (B).
  • the mixture according to this embodiment refers to one that substantially contains only the polyoxyalkylene polymers (A) and (B). Since the polyoxyalkylene polymers (A) and (B) each have a hydrolyzable silyl group, the mixture exhibits curability based on hydrolysis and dehydration condensation reactions of the hydrolyzable silyl group.
  • Both polyoxyalkylene polymers (A) and (B) have a main chain structure of polyoxyalkylene and a terminal structure bonded to the end of the main chain structure, and the terminal structure is a hydrolyzable silyl. group and a terminal olefinic group and/or an internal olefinic group.
  • the main chain structure refers to a polymer main chain (also referred to as a polymer skeleton) composed of oxyalkylene repeating units.
  • the oxyalkylene repeating unit refers to a repeating unit constituting a polyether, and refers to, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
  • the main chain structure is not particularly limited and includes, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer. Examples include merging. Among them, polyoxypropylene is preferred.
  • linear main chain structure described below refers to a main chain structure that is linear.
  • branched main chain structure described below refers to a main chain structure that is branched.
  • the number average molecular weight and weight average molecular weight in this specification are polystyrene equivalent molecular weights obtained by gel permeation chromatography (GPC) measurement using tetrahydrofuran (THF) as a developing solvent.
  • the molecular weight distribution is a value calculated from the number average molecular weight and the weight average molecular weight, and is the value obtained by dividing the weight average molecular weight by the number average molecular weight.
  • the terminal structure refers to a site located at the end of the polyoxyalkylene polymer. Further, the terminal structure has a hydrolyzable silyl group, a terminal olefin group, and/or an internal olefin group. Examples of the terminal olefin group include an active hydrogen group-containing group and an unsaturated group. As the active hydrogen-containing group, a hydroxyl group is preferred. The unsaturated group is preferably an allyl group or a methallyl group, and more preferably an allyl group.
  • the polyoxyalkylene polymers (A) and (B) have a hydrolyzable silyl group.
  • the hydrolyzable silyl group refers to a silicon group that has a hydroxyl group or a hydrolyzable group on a silicon atom and can form a siloxane bond through a hydrolysis/condensation reaction. Specifically, it is represented by the following general formula (2).
  • R 2 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by -OSi(R') 3 .
  • R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different.
  • X represents a hydroxyl group or a hydrolyzable group, When two or more Xs exist, they may be the same or different.
  • a is 1, 2 or 3).
  • the hydrocarbon group of R 2 preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • Specific examples of R 3 include, for example, a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N,N-diethylaminomethyl group. Preferred are methyl group, ethyl group, chloromethyl group, and methoxymethyl group, more preferred are methyl group and methoxymethyl group.
  • the hydrolyzable silyl group possessed by the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) includes a structure represented by the following general formula (1).
  • -R 1 -CH 2 -CH 2 -Si(R 2 3-a )X a (1)
  • R 1 represents a divalent organic group having 1 to 20 carbon atoms containing one or more constituent atoms selected from the group consisting of hydrogen, carbon, and nitrogen
  • R 2 , X, and a are The formula (2) is as described above.
  • R 1 is preferably CH 2 and a is 2.
  • the hydrolyzable group of the above X is not particularly limited, and may be any conventionally known hydrolyzable group. Specific examples 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 group. Among these, alkoxy groups such as methoxy group and ethoxy group are more preferable, and methoxy group and ethoxy group are particularly preferable because they are mildly hydrolyzable and easy to handle.
  • the hydrolyzable silyl group includes a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a dimethoxyethyl group.
  • Silyl group (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, ( Examples include, but are not limited to, N,N-diethylaminomethyl)diethoxysilyl group.
  • methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N- A diethylaminomethyl) dimethoxysilyl group is preferred because it exhibits high activity and provides a cured product with good mechanical properties.
  • Methyldimethoxysilyl group is preferred because it has excellent shape retention after coating.
  • a trimethoxysilyl group is preferred because it exhibits good initial strength and provides a cured product with high rigidity.
  • the polyoxyalkylene polymer (A) has a linear main chain structure. Moreover, the polyoxyalkylene polymer (A) has only one terminal structure in one molecule.
  • Such a polyoxyalkylene polymer (A) is obtained by ring-opening addition polymerization of an alkylene oxide monomer to an initiator having one active hydrogen in the presence of an alkylene oxide ring-opening polymerization catalyst.
  • the polyoxyalkylene polymer (A) has a linear structure, but is composed of only a main chain structure containing an initiator and an oxyalkylene repeating unit, and one terminal structure.
  • the active hydrogen in the initiator is preferably based on a hydroxyl group.
  • the initiator may be a compound having one active hydrogen, preferably a compound having one hydroxyl group.
  • Specific examples of compounds having one hydroxyl group include methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene monomethyl ether, and triethylene monomethyl ether.
  • propylene glycol monomethyl ether propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene monomethyl ether, tripropylene monomethyl ether, allyl alcohol, ethylene glycol monoallyl ether, and the like.
  • butanol is particularly preferred.
  • an initiator may be synthesized from the compound having one hydroxyl group and an alkylene oxide monomer.
  • the synthesized initiator is obtained by ring-opening addition polymerization of an alkylene oxide monomer to the compound having one hydroxyl group, and preferably has a number average molecular weight of 100 to 10,000.
  • One type of initiator may be used alone or two or more types may be used in combination.
  • the polyoxyalkylene polymer (A) only needs to have one terminal in one molecule, and has one or less hydrolyzable silyl group on average in one terminal structure. It may have more than one hydrolyzable silyl group. Furthermore, one terminal structure may contain a polyoxyalkylene having two or more hydrolyzable silyl groups.
  • the terminal structure having two or more hydrolyzable silyl groups can be represented by the following general formula (3), for example.
  • R 3 and R 5 each independently represent a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to each carbon atom adjacent to R 3 and R 5 are carbon, oxygen, nitrogen, R 4 and R 6 each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
  • n is an integer of 1 to 10.
  • R 2 , X, and a are any of the above-mentioned general (Formula (1) is as described above.)
  • R 3 and R 5 may be a divalent organic group having 1 to 6 carbon atoms, or a hydrocarbon group which may contain an oxygen atom.
  • the hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms.
  • Specific examples of R 3 include -CH 2 OCH 2 -, -CH 2 O-, and -CH 2 -, with preference given to -CH 2 OCH 2 -.
  • Specific examples of R 5 include -CH 2 - and -CH 2 CH 2 -, with -CH 2 - being preferred.
  • the number of carbon atoms in the hydrocarbon group of R 4 and R 6 is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.
  • Specific examples of R 4 and R 6 include a hydrogen atom, a methyl group, and an ethyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • R 3 is -CH 2 OCH 2 -
  • R 5 is -CH 2 -
  • R 4 and R 6 are each a hydrogen atom. It is.
  • n is preferably an integer of 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
  • n is not limited to one value, and may be a mixture of a plurality of values.
  • the terminal structure represented by general formula (3) represents one terminal structure bonded to one terminal of the main chain structure. Although two or more reactive silyl groups are shown in formula (3), formula (3) does not indicate two or more terminals, but rather two or more reactive silyl groups in one terminal structure. This indicates the presence of a silyl group. Further, formula (3) does not include a main chain structure (polymer skeleton) composed of oxyalkylene repeating units. In other words, the n structures in parentheses in formula (3) do not correspond to oxyalkylene repeating units in the main chain structure (polymer skeleton).
  • number of moles of hydrolyzable silyl group/(total number of moles of hydrolyzable silyl group, terminal olefin group, and internal olefin group) is 0.50 or more, 1. It is preferably less than 0.00, more preferably 0.70 or more and less than 1.00.
  • number of moles of hydrolyzable silyl group/(total number of moles of hydrolyzable silyl group, terminal olefin group, and internal olefin group) means that the number of moles of hydrolyzable silyl group is means the ratio of terminal olefin groups and internal olefin groups to the total number of moles.
  • hydrolyzable silyl group introduction rate can also be expressed as "hydrolyzable silyl group introduction rate.” Further, the ratio can also be expressed as a percentage; for example, the ratio of 0.5 and 50% have the same meaning.
  • the ratio can be determined by 1 H NMR.
  • the terminal olefin group is an allyl group and a hydrolyzable silyl group is introduced into the terminal structure by subjecting a hydrosilane compound having a hydrolyzable silyl group to a hydrosilylation reaction as described below, each of the following signals Calculation can be done using an integral value.
  • ⁇ Hydrolyzable silyl group CH 2 bonded to the silyl group (around 0.6 ppm, 2H)
  • ⁇ Terminal olefin group CH 2 of methylidene group (around 5.2 ppm, 2H)
  • Internal olefin group CH bonded to the terminal CH 3 group (total of around 4.3 ppm and around 4.8 ppm, 1H) Note that when other signals overlap, the integral value of that signal is excluded from calculation.
  • the number average molecular weight of the polyoxyalkylene polymer (A) may be 1,000 or more and 8,000 or less, but is preferably 2,000 or more and 5,000 or less in terms of polystyrene equivalent molecular weight in GPC. Within the latter range, the adhesive strength will increase quickly and the curable composition will have good workability.
  • the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, specifically less than 2.0, more preferably 1.6 or less, 1. It is more preferably 5 or less, even more preferably 1.4 or less, and particularly preferably 1.2 or less.
  • the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
  • the polyoxyalkylene polymer (A) may have a hydrolyzable silyl group in addition to the terminal structure, but having it only in the terminal structure will result in a rubber-like cured product with high elongation and low elastic modulus. This is preferred because it is easier to obtain.
  • the method for synthesizing the polyoxyalkylene polymer (A) is not particularly limited.
  • an epoxy compound is polymerized with an initiator having a hydroxyl group to obtain a hydroxyl group-terminated polymer.
  • an alkali metal salt e.g., sodium methoxide
  • a halogenated hydrocarbon compound e.g., allyl chloride
  • a hydrolyzable silyl group-containing polyoxyalkylene polymer (A) can be obtained by reacting a hydrolyzable silyl group-containing hydrosilane compound (for example, dimethoxymethylsilane, trimethoxysilane).
  • a hydrolyzable silyl group-containing hydrosilane compound for example, dimethoxymethylsilane, trimethoxysilane.
  • a polyoxyalkylene polymer (A) containing a polyoxyalkylene polymer having two or more hydrolyzable silyl groups in one terminal structure which is a preferred embodiment, is obtained as follows. be able to. After the alkali metal salt is made to act on the hydroxyl group of the hydroxyl group-terminated polymer in the same manner as above, an epoxy compound having a carbon-carbon unsaturated bond (for example, allyl glycidyl ether) is reacted, and then the carbon-carbon unsaturated bond is reacted with the epoxy compound (for example, allyl glycidyl ether).
  • an epoxy compound having a carbon-carbon unsaturated bond for example, allyl glycidyl ether
  • Two or more carbon-carbon unsaturated bonds are introduced into one terminal by reacting a halogenated hydrocarbon compound (for example, allyl chloride) having a saturated bond. Thereafter, a hydrolyzable silyl group-containing hydrosilane compound may be reacted.
  • a halogenated hydrocarbon compound for example, allyl chloride
  • hydrolysable silyl group into the polymer by using a hydrolysable silyl group-containing mercaptosilane instead of the hydrolysable silyl group-containing hydrosilane compound.
  • a cured product obtained from a curable composition containing a polyoxyalkylene polymer (A) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonds, etc.
  • the polyoxyalkylene polymer (A) containing an amide segment or the like may be cleaved by heat or the like.
  • a curable composition containing a polyoxyalkylene polymer (A) containing an amide segment or the like tends to have a high viscosity.
  • polyoxyalkylene containing amide segments etc. may be used as the polyoxyalkylene polymer (A), or polyoxyalkylene containing no amide segments etc. may be used. You may.
  • the amide segment represented by the general formula (4) includes, for example, a reaction between an isocyanate group and a hydroxyl group, a reaction between an amino group and a carbonate, a reaction between an isocyanate group and an amino group, a reaction between an isocyanate group and a mercapto group. Examples include those formed by, etc. Moreover, those formed by the reaction of the above-mentioned amide segment containing an active hydrogen atom with an isocyanate group are also included in the amide segment represented by the general formula (4).
  • An example of a method for producing a polyoxyalkylene polymer (A) containing an amide segment is to react a polyoxyalkylene having an active hydrogen-containing group at the end with a polyisocyanate compound to form a polyoxyalkylene polymer having an isocyanate group at the end.
  • a functional group that can react with the isocyanate group for example, a hydroxyl group, a carboxy group, a mercapto group, a primary amino group, or a secondary amino group
  • Examples include methods of reacting compounds.
  • Another example is a method in which a polyoxyalkylene having an active hydrogen-containing group at its terminal is reacted with a hydrolyzable silyl group-containing isocyanate compound.
  • the number (average value) of amide segments per molecule of the polyoxyalkylene polymer (A) is preferably 1 to 10, and 1.5 to 5. is more preferred, and 2 to 3 are particularly preferred. If this number is less than 1, the curability may not be sufficient, and if it is greater than 10, the polyoxyalkylene polymer (A) may have a high viscosity and become difficult to handle. There is. In order to lower the viscosity of the curable composition and improve workability, the polyoxyalkylene polymer (A) preferably does not contain an amide segment.
  • the polyoxyalkylene polymer (B) has a branched main chain structure.
  • Such a polyoxyalkylene polymer (B) is obtained by ring-opening addition polymerization of an alkylene oxide monomer to an initiator having three or more active hydrogen atoms in the presence of an alkylene oxide ring-opening polymerization catalyst. is preferred.
  • the active hydrogen in the initiator is preferably based on a hydroxyl group.
  • the initiator may be a compound having three or more active hydrogens, and preferably a compound having three or more hydroxyl groups.
  • Specific examples of compounds having three or more hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, sorbitol, and pentaerythritol. Among these, glycerin is particularly preferred.
  • an initiator may be synthesized using the compound having three or more hydroxyl groups and an alkylene oxide monomer.
  • the synthesized initiator is obtained by ring-opening addition polymerization of an alkylene oxide monomer to the compound having three hydroxyl groups, and preferably has a number average molecular weight of 100 to 10,000.
  • One type of initiator may be used alone or two or more types may be used in combination.
  • the polyoxyalkylene polymer (B) preferably has 1 to 4 branched chains from the viewpoint of availability of raw materials, and most preferably has 1 branched chain because good strength and elongation can be obtained.
  • the polyoxyalkylene polymer (B) may have hydrolyzable silyl groups in a plurality of terminal structures among the terminal structures present in one molecule. Moreover, it may have one or less hydrolyzable silyl groups on average in one terminal structure, or it may contain polyoxyalkylene having two or more hydrolyzable silyl groups in one terminal structure. It's okay if it is.
  • the terminal structure having two or more hydrolyzable silyl groups can be represented by the above general formula (3), for example.
  • the general formula (3), terminal structure, etc. are the same as those for the polyoxyalkylene polymer (A) described above.
  • polyoxyalkylene polymer (B) "number of moles of hydrolyzable silyl group/(total number of moles of hydrolyzable silyl group, terminal olefin group, and internal olefin group)" is 0.60 or more, 1. It is preferably less than 0.00, more preferably 0.70 or more and less than 1.00.
  • the explanation of the formula etc. is the same as that of the polyoxyalkylene polymer (A) mentioned above.
  • the number average molecular weight of the polyoxyalkylene polymer (B) may be 6,000 or more and 15,000 or less, but is preferably 9,000 or more and 14,000 or less in terms of polystyrene equivalent molecular weight in GPC. Within the latter range, adhesive strength develops quickly and workability when handling the curable composition can be improved.
  • the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (B) is not particularly limited, but is preferably narrow, specifically less than 2.0, more preferably 1.6 or less, 1. It is more preferably 5 or less, even more preferably 1.4 or less, and particularly preferably 1.2 or less.
  • the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (B) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
  • the polyoxyalkylene polymer (B) may have a hydrolyzable silyl group in addition to the terminal structure, but having it only in the terminal structure will result in a rubber-like cured product with high elongation and low elastic modulus. This is preferred because it is easier to obtain.
  • the method for synthesizing the polyoxyalkylene polymer (B) is not particularly limited.
  • an epoxy compound is polymerized with an initiator having a hydroxyl group to obtain a hydroxyl group-terminated polymer.
  • an alkali metal salt e.g., sodium methoxide
  • a halogenated hydrocarbon compound e.g., allyl chloride
  • hydrolyzable silyl group-containing hydrosilane compound for example, dimethoxymethylsilane, trimethoxysilane
  • a hydrolyzable silyl group-containing polyoxyalkylene polymer (B) can be obtained.
  • a polyoxyalkylene polymer (B) containing a polyoxyalkylene polymer having two or more hydrolyzable silyl groups in one terminal structure which is a preferred embodiment, can be obtained as follows. be able to. After the alkali metal salt is made to act on the hydroxyl group of the hydroxyl group-terminated polymer in the same manner as above, an epoxy compound having a carbon-carbon unsaturated bond (for example, allyl glycidyl ether) is reacted, and then the carbon-carbon unsaturated bond is reacted with the epoxy compound (for example, allyl glycidyl ether).
  • an epoxy compound having a carbon-carbon unsaturated bond for example, allyl glycidyl ether
  • Two or more carbon-carbon unsaturated bonds are introduced into one terminal by reacting a halogenated hydrocarbon compound (for example, allyl chloride) having a saturated bond. Thereafter, a hydrolyzable silyl group-containing hydrosilane compound may be reacted.
  • a halogenated hydrocarbon compound for example, allyl chloride
  • hydrolysable silyl group into the polymer by using a hydrolysable silyl group-containing mercaptosilane instead of the hydrolysable silyl group-containing hydrosilane compound.
  • the main chain structure of the polyoxyalkylene polymer (B) may include an ester bond or an amide segment represented by general formula (4).
  • a cured product obtained from a curable composition containing a polyoxyalkylene polymer (B) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonds, etc.
  • the polyoxyalkylene polymer (B) containing an amide segment or the like may be cleaved by heat or the like.
  • a curable composition containing a polyoxyalkylene polymer (B) containing an amide segment or the like tends to have a high viscosity.
  • polyoxyalkylene containing amide segments etc. may be used as the polyoxyalkylene polymer (B), or polyoxyalkylene containing no amide segments etc. may be used. You may.
  • the amide segment represented by the general formula (4) includes, for example, a reaction between an isocyanate group and a hydroxyl group, a reaction between an amino group and a carbonate, a reaction between an isocyanate group and an amino group, a reaction between an isocyanate group and a mercapto group. Examples include those formed by, etc. Moreover, those formed by the reaction of the above-mentioned amide segment containing an active hydrogen atom with an isocyanate group are also included in the amide segment represented by the general formula (4).
  • An example of a method for producing a polyoxyalkylene polymer (B) containing an amide segment is to react a polyoxyalkylene having an active hydrogen-containing group at the end with a polyisocyanate compound to form a polyoxyalkylene polymer having an isocyanate group at the end.
  • a functional group that can react with the isocyanate group for example, a hydroxyl group, a carboxy group, a mercapto group, a primary amino group, or a secondary amino group
  • Examples include methods of reacting compounds.
  • Another example is a method in which a polyoxyalkylene having an active hydrogen-containing group at its terminal is reacted with a hydrolyzable silyl group-containing isocyanate compound.
  • the number (average value) of amide segments per molecule of the polyoxyalkylene polymer (B) is preferably 1 to 10, and 1.5 to 5. is more preferred, and 2 to 3 are particularly preferred. If this number is less than 1, the curability may not be sufficient, and if it is greater than 10, the polyoxyalkylene polymer (B) may have a high viscosity and become difficult to handle. There is. In order to lower the viscosity of the curable composition and improve workability, the polyoxyalkylene polymer (B) preferably does not contain an amide segment.
  • the weight ratio of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) (A):(B) is preferably 5:95 to 60:40, and 10:90 to The ratio is more preferably 40:60, and even more preferably 10:90 to 25:75.
  • the mass ratio of the contents of the polyoxyalkylene polymers (A) and (B) is within the above range, the adhesive strength tends to rise quickly.
  • the viscosity at 23°C of the mixture containing the polyoxyalkylene polymers (A) and (B) is preferably 0.5 Pa ⁇ s to 5.0 Pa ⁇ s, and preferably 1.0 Pa ⁇ s to 3.5 Pa ⁇ s. - It is more preferable that it is s.
  • the viscosity of the mixture of polyoxyalkylene polymers (A) and (B) is within the above range, the adhesive strength tends to rise quickly.
  • the polyoxyalkylene polymers (A) and (B) may be polymerized by mixing their respective initiators in advance during polymerization, or may be mixed at the time of polymer synthesis, or may be polymerized using a curable composition. When manufacturing a product, it can be mixed in advance, or it can be mixed at the time of construction.
  • the present invention can provide a curable composition containing a mixture containing the polyoxyalkylene polymers (A) and (B).
  • the composition of the present invention contains additives such as a silanol condensation catalyst, a filler, an adhesion promoter, a plasticizer, a solvent, a diluent, and a sauce. Addition of inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, physical property regulators, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen curing substances, epoxy resins, and other resins. It's okay. Furthermore, various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or cured product.
  • additives such as a silanol condensation catalyst, a filler, an adhesion promoter, a plasticizer, a solvent, a diluent, and a sauce. Addition of inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, physical property regulators, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen curing substances, epoxy resins, and other resin
  • additives include, for example, surface improvers, blowing agents, curing modifiers, flame retardants, silicates, radical inhibitors, metal deactivators, antiozonants, phosphorous peroxides, etc.
  • examples include decomposers, lubricants, pigments, and fungicides.
  • ⁇ Silanol condensation catalyst> the reaction of hydrolyzing and condensing the hydrolysable silyl groups of polyoxyalkylene polymers (A) and (B) having hydrolysable silyl groups is promoted, that is, the curing reaction is promoted, and the polymer chain is extended.
  • a silanol condensation catalyst may be used for the purpose of crosslinking.
  • silanol condensation catalyst such as organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, and inorganic acids.
  • organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), and dioctyltin bis(acetylacetonate).
  • dioctyltin dilaurate dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, reaction product of dibutyltin oxide and silicate compound, reaction product of dioctyltin oxide and silicate compound, dibutyltin oxide and phthalate ester
  • Examples include reactants of
  • carboxylic acid metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, calcium carboxylate, and the like.
  • carboxylic acid group the following carboxylic acids and various metals can be combined.
  • amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; butyl biguanide, 1-o-tolyl biguanide, and 1- Examples include biguanides such as phenylbiguanide; amino group-containing silane coupling agents; ketimine compounds.
  • amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine
  • pyridine 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing
  • carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
  • alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), diisopropoxy titanium bis (ethylacetocetate), aluminum tris (acetylacetonate), diisopropoxyaluminum ethylacetonate, etc.
  • titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), diisopropoxy titanium bis (ethylacetocetate), aluminum tris (acetylacetonate), diisopropoxyaluminum ethylacetonate, etc.
  • aluminum compounds such as acetate
  • zirconium compounds such as zirconium tetrakis (acetylacetonate).
  • fluorine anion-containing compounds As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.
  • silanol condensation catalyst Only one type of silanol condensation catalyst may be used, or two or more types may be used in combination.
  • the above-mentioned amine compound and carboxylic acid, or the combination of the amine compound, carboxylic acid, and alkoxy metal Therefore, the effect of improving reactivity may be obtained.
  • the amount of the silanol condensation catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, based on 100 parts by weight of the mixture of polyoxyalkylene polymers (A) and (B). is more preferable, and 0.01 to 10 parts by weight is particularly preferable.
  • Fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, calcined clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, and hydrated silica.
  • Examples include silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, and filament.
  • the above-mentioned fillers may be used alone or in a mixture of two or more.
  • the amount of filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B).
  • An organic balloon or an inorganic balloon may be added for the purpose of making the composition lighter (lower specific gravity).
  • the balloon is made of a spherical filler and is hollow inside, and examples of the material for the balloon include inorganic materials such as glass and shirasu, and organic materials such as phenol resin, urea resin, polystyrene, and saran.
  • the amount of the balloon used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B). .
  • An adhesion imparting agent can be added to the curable composition according to this embodiment.
  • the adhesion imparting agent include an amino group-containing silane coupling agent, an isocyanate group-containing silane coupling agent, a mercapto group-containing silane coupling agent, and an epoxy group-containing silane coupling agent.
  • the amino group-containing silane coupling agent is a compound that has both an amino group and a hydrolyzable silyl group. Specific examples include, but are not limited to, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisopropoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane.
  • ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriethoxysilane, ⁇ -(2-aminoethyl) ) Aminopropylmethyldiethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriisopropoxysilane, ⁇ -(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyl Trimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, ⁇ -ure
  • adhesive properties include ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane, ⁇ -isocyanatemethyltrimethoxysilane, ⁇ -isocyanatemethyldimethoxymethyl Isocyanate group-containing silanes such as silane; mercapto group-containing silanes such as ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, Examples include epoxy group-containing silanes such as ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
  • reactants of various silane coupling agents can also be used. Only one type of adhesion imparting agent may be used, or two or more types may be used in combination.
  • the amount of adhesion imparting agent used is preferably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B). Parts by weight are more preferred.
  • the adhesion imparting agent is preferably an amino group-containing silane coupling agent, and the amount used is preferably 0.5 to 10 parts by weight.
  • plasticizer can be added to the curable composition according to this embodiment.
  • plasticizers include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butylbenzyl phthalate; bis(2-ethylhexyl); )-Terephthalate ester compounds such as 1,4-benzenedicarboxylate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyhydric carboxylic acid ester compounds such as acetyl tributyl citrate; unsaturated fatty acid ester compounds such
  • polymer plasticizers can be used.
  • polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or more; Examples include polyethers such as derivatives converted into polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like.
  • the amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B). Particularly preferred is 20 to 100 parts by weight. If it is less than 5 parts by weight, it will not be effective as a plasticizer, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient. Plasticizers may be used alone or in combination of two or more.
  • Solvents or diluents can be added to the compositions of the invention.
  • the solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, and the like can be used.
  • the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, particularly preferably 250°C or higher, in view of the problem of air pollution when the composition is used indoors.
  • the above solvents or diluents may be used alone or in combination of two or more.
  • Anti-sagging agent may be added to the curable composition according to this embodiment in order to prevent sagging and improve workability.
  • Anti-sagging agents include, but are not particularly limited to, polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
  • the amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B).
  • antioxidant antioxidant agent
  • Use of an antioxidant can improve the heat resistance and weather resistance of the cured product.
  • antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
  • the antioxidant in the mixture and curable composition according to the present embodiment is preferably a hindered phenol type antioxidant, and the amount used is 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B).
  • the amount is preferably 0.05 to 10.00 parts by weight, more preferably 0.1 to 5.0 parts by weight, and particularly preferably 0.2 to 2.5 parts by weight.
  • a light stabilizer may be added to the curable composition according to this embodiment.
  • Use of a light stabilizer can prevent photooxidative deterioration of the cured product.
  • Examples of light stabilizers include benzotriazole compounds, hindered amine compounds, and benzoate compounds, and hindered amine compounds are particularly preferred.
  • the amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B). part is more preferable.
  • a UV absorber may be added to the curable composition according to this embodiment.
  • Use of an ultraviolet absorber can improve the surface weather resistance of the cured product.
  • the ultraviolet absorber include benzophenone, benzotriazole, salicylate, substituted acrylonitrile, and metal chelate compounds. Particularly preferred are benzotriazoles, and commercially available names include Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
  • the amount of ultraviolet absorber used is preferably 0.1 to 10 parts by weight, and preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B). part is more preferable.
  • the curable composition of the present invention may optionally contain a physical property modifier for adjusting the tensile properties of the resulting cured product.
  • Physical property modifiers are not particularly limited, but include, for example, alkyl alkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane Aryl alkoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane; tris(trimethylsilyl)borate, tris(triethyl Trialkylsilyl borates such as silyl) borates; silicone varnishes; polysiloxanes, and
  • the physical property modifier By using the physical property modifier, it is possible to increase the hardness of the composition of the present invention when it is cured, or conversely to decrease the hardness and increase the elongation at break.
  • the above physical property modifiers may be used alone or in combination of two or more.
  • a compound that produces a compound having a monovalent silanol group in its molecule upon hydrolysis has the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product.
  • Particularly preferred are compounds that produce trimethylsilanol.
  • Examples of compounds that produce compounds having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which produce silane monomers by hydrolysis. Mention may be made of silicon compounds that produce ol. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.
  • the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, and preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B). part is more preferable.
  • a tackifying resin can be added for the purpose of improving adhesion or adhesion to a base material, or for other purposes as necessary.
  • tackifying resin There are no particular restrictions on the tackifying resin, and commonly used tackifying resins can be used.
  • terpene resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumaron-indene resins, and rosin-based resins.
  • the amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B). More preferably, the amount is between 30 parts and 30 parts. If it is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion effects to the substrate, and if it exceeds 100 parts by weight, the viscosity of the composition may become too high, making it difficult to handle.
  • Compounds containing epoxy groups can be used in the compositions of the invention. When a compound having an epoxy group is used, the restorability of the cured product can be improved.
  • compounds having an epoxy group include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate , epoxybutyl stearate, etc.
  • the epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B).
  • Photocurable materials can be used in the compositions of the present invention.
  • a photocurable material When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved.
  • Many compounds of this type are known, including organic monomers, oligomers, resins, and compositions containing them.A typical example is one containing one or several acrylic or methacrylic unsaturated groups. Unsaturated acrylic compounds, polyvinyl cinnamates, azidated resins, etc., which are monomers, oligomers, or mixtures thereof, can be used.
  • the amount of photocurable substance used is in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of polyoxyalkylene polymers (A) and (B). If it is less than 0.1 part by weight, there is no effect of improving weather resistance, and if it is more than 20 parts by weight, the cured product becomes too hard and tends to crack.
  • Oxygen curable materials can be used in the compositions of the present invention.
  • oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which reacts with oxygen in the air to form a cured film near the surface of the cured product, causing stickiness on the surface and dust on the surface of the cured product. It acts by preventing the adhesion of dirt and dust.
  • Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these compounds; acrylic polymers and epoxy resins modified with drying oils.
  • silicone resin 1,2-polybutadiene, 1,4-polybutadiene, C5 to C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
  • diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
  • liquid polymers These may be used alone or in combination of two or more.
  • the amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, and more preferably, based on 100 parts by weight of the total amount of the polyoxyalkylene polymers (A) and (B).
  • the amount is 0.5 to 10 parts by weight. If the amount used is less than 0.1 part by weight, the improvement in staining properties will not be sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product will tend to be impaired.
  • oxygen-curable substances are preferably used in combination with photo-curable substances.
  • Epoxy resin may be added to the curable composition according to this embodiment.
  • Compositions containing epoxy resins are particularly preferred as adhesives for exterior wall tiles.
  • the epoxy resin include bisphenol A type epoxy resins and novolac type epoxy resins.
  • a curing agent for curing the epoxy resin can be used in combination with the adhesive composition according to the present embodiment.
  • the epoxy resin curing agent that can be used, and commonly used epoxy resin curing agents can be used.
  • the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.
  • curable compositions have been known that are a blend of polyoxyalkylene polymers (A) and (B) having hydrolyzable silyl groups and (meth)acrylic polymers having hydrolyzable silyl groups. .
  • the curable composition according to the present embodiment may contain a (meth)acrylic polymer having a hydrolyzable silyl group, but it may not substantially contain the (meth)acrylic polymer. It's okay. Even when the (meth)acrylic polymer is not substantially contained, the adhesion to the polyester base material can be improved. In addition, when the (meth)acrylic polymer is not substantially contained, the curable composition can have a low viscosity, which provides the advantage of good workability.
  • the content of the (meth)acrylic polymer having a hydrolyzable silyl group may be 0 to 10 parts by weight based on 100 parts by weight of the total amount of the polyoxyalkylene polymers (A) and (B). , 0 to 5 parts by weight, or 0 to 1 part by weight. Further, the amount may be less than 1 part by weight, or less than 0.1 part by weight.
  • ⁇ Weight ratio of polyoxyalkylene polymers (A) and (B) in curable composition >>
  • the weight ratio of the total content of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) in the curable composition is 15% when the total weight of the curable composition is 100%. It is preferably 50%, more preferably 20% to 35%. When the weight ratio of the total content of (A) and (B) is within the above range, curability is good and the rate of development of adhesive strength is likely to be excellent.
  • the viscosity of the curable composition containing the polyoxyalkylene polymers (A) and (B) at 23° C. is preferably 30 Pa ⁇ s to 400 Pa ⁇ s at a rotation speed of 10 rpm using a B-type viscometer.
  • the viscosity of the curable composition containing the polyoxyalkylene polymers (A) and (B) is within the above range, it will have good workability, excellent mechanical properties, and an excellent rate of development of adhesive strength. Cheap.
  • the curable composition of the present invention can also be prepared as a one-component type in which all the ingredients are mixed in advance and stored in a sealed container, and the composition is cured by moisture in the air after application. It is also possible to prepare a two-component product in which components such as a filler, a plasticizer, and water are mixed in advance and the blended materials and the organic polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.
  • the curable composition is a one-component type
  • all components are blended in advance, so components containing water are either dehydrated and dried before use, or dehydrated during compounding and kneading by reducing pressure, etc. is preferable.
  • Storage stability is further improved by adding an alkoxysilane compound such as silane or ⁇ -glycidoxypropyltrimethoxysilane.
  • the dehydrating agent partially condensed silane compounds such as Dynasylan 6490 manufactured by Evonik can also be suitably used from the viewpoint of safety and stability.
  • the amount of a dehydrating agent, particularly a silicon compound capable of reacting with water such as vinyltrimethoxysilane, to be used is 0.00 parts by weight based on 100 parts by weight of the total amount of the polyoxyalkylene polymers (A) and (B) of the present invention. It is preferably used in a range of 1 to 20 parts by weight, more preferably in a range of 0.5 to 10 parts by weight.
  • the polyoxyalkylene polymers (A) and (B) may be mixed in advance, or may be added and mixed when producing the curable composition, or may be added and mixed at the time of construction. You can also do that.
  • the method of pre-mixing the polyoxyalkylene polymers (A) and (B) is not particularly specified, but for example, the polyoxyalkylene polymers (A) and (B) are placed in a container equipped with a hook or stirring blade, and the A method of mixing with a stirrer or a stirring blade, or a method of mixing polyoxyalkylene polymers (A) and (B) in a container and mixing with a drill mixer or a stirrer, or a method of mixing polyoxyalkylene polymers (A) and (B) in a container. by mechanical mixing using a rotation-revolution mixer, or by convection by vigorously adding the other polyoxyalkylene polymer to the container containing polyoxyalkylene polymer (A) or (B). There are methods of mixing. If the amount is small, it can also be mixed by hand with a spatula or spatula. In any method, the mixing is preferably carried out under heating, at room temperature, or under cooling.
  • the curable composition of the present invention is suitable for adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, coating film waterproofing materials, molding agents, vibration-proofing materials, damping materials, and soundproofing materials. , can be used as foam material, paint, spray material. Since the cured product obtained by curing the curable composition of the present invention has excellent flexibility and adhesive properties, it can be suitably used as a sealant or adhesive.
  • the curable composition of the present invention can be used for electrical/electronic component materials such as solar cell back sealing materials, electrical/electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for devices, acoustic insulating materials, Elastic adhesives, binders, contact adhesives, spray sealants, crack repair materials, tiling adhesives, asphalt waterproofing adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives , medical adhesive sheets, medical device sealants, dental impression materials, food packaging materials, joint sealants for exterior materials such as sizing boards, coating materials, anti-slip covering materials, cushioning materials, primers, conductive materials for shielding electromagnetic waves, Thermal conductive materials, hot melt materials, electrical and electronic potting agents, films, gaskets, concrete reinforcing materials, temporary fixing adhesives, various molding materials, and rust prevention and cutting of wired glass and laminated glass edges (cut parts).
  • electrical/electronic component materials such as solar cell back sealing materials, electrical/electronic
  • waterproof sealants Used for various purposes such as waterproof sealants, liquid sealants used in automobile parts, large vehicle parts such as trucks and buses, train car parts, aircraft parts, marine parts, electrical parts, various mechanical parts, etc. It is possible. Taking automobiles as an example, it can be used in a wide variety of applications, such as attaching plastic covers, trims, flanges, bumpers, windows, and adhesively attaching interior and exterior parts. Furthermore, it can be used alone or with the aid of a primer to adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc., and thus can be used in various types of sealing and adhesive compositions. .
  • the curable composition of the present invention can be used for interior panel adhesives, exterior panel adhesives, tiling adhesives, masonry adhesives, ceiling finishing adhesives, floor finishing adhesives, and wall finishing adhesives.
  • Adhesives adhesives for vehicle panels, adhesives for electrical, electronic and precision equipment assembly, adhesives for bonding leather, textiles, fabrics, paper, boards and rubber, reactive post-crosslinking pressure-sensitive adhesives, direct It can also be used as a sealant for glazing, a sealant for double-glazed glass, a sealant for SSG construction, a sealant for working joints in buildings, and a material for civil engineering and bridges.
  • it can be used as an adhesive material such as adhesive tape or adhesive sheet.
  • [Item 2] The mixture according to item 1, wherein the main chain structure of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) is polyoxypropylene.
  • [Item 3] The mixture according to item 1 or 2, wherein the polyoxyalkylene polymer (B) has a number average molecular weight of 9,000 or more and 14,000 or less.
  • [Item 4] The mixture according to any one of items 1 to 3, wherein the viscosity of the mixture is 1.0 Pa ⁇ s or more and 3.5 Pa ⁇ s or less.
  • [Item 5] The mixture according to any one of items 1 to 4, wherein the polyoxyalkylene polymer (A) has a number average molecular weight of 2,000 or more and 5,000 or less.
  • the hydrolyzable silyl group has the general formula (1): -R 1 -CH 2 -CH 2 -Si(R 2 3-a )X a (1) (In the formula, R 1 represents a divalent organic group having 1 to 20 carbon atoms and containing one or more constituent atoms selected from the group consisting of hydrogen, carbon, and nitrogen, and R 2 represents a divalent organic group having 1 to 20 carbon atoms.
  • the number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
  • Liquid feeding system Tosoh HLC-8420GPC
  • Column Tosoh TSK-GEL H type
  • Solvent THF
  • the hydrolyzable silyl group introduction rate in the examples was calculated using the results of 1 H-NMR measurement (measured in CDCl 3 solvent) using the following nuclear magnetic resonance apparatus (NMR). . In this calculation, the calculation method described above was used.
  • allyl glycidyl ether was added to the hydroxyl groups of the polymer (P-1), and a reaction was carried out at 130° C. for 2 hours. Thereafter, 0.28 molar equivalent of a methanol solution of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was further added to convert the hydroxyl group to an allyl group.
  • polyoxypropylene (Q-1) having an allyl group in only one terminal structure was obtained.
  • 50 ⁇ l of platinum divinyldisiloxane complex (3% by weight 2-propanol solution in terms of platinum) was added, and while stirring, 23.5 g of dimethoxymethylsilane was slowly added dropwise. After reacting the mixed solution at 100°C for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain 1.
  • Polyoxypropylene (polymer A-1) having only one terminal structure in the molecule was obtained.
  • Synthesis example 7 Polyoxypropylene triol with a number average molecular weight of about 4,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to produce a polymer with a branched main chain structure and a hydroxyl group, a number average molecular weight of 11,000, and a molecular weight distribution Mw.
  • allyl glycidyl ether was added to the hydroxyl groups of the polymer (P-7), and a reaction was carried out at 130° C. for 2 hours. Thereafter, 0.28 molar equivalent of a methanol solution of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was further added to convert the terminal hydroxyl group to an allyl group.
  • polyoxypropylene (Q-7) having an allyl group at the terminal structure was obtained.
  • a platinum divinyldisiloxane complex solution (a 3% by weight isopropanol solution in terms of platinum) was added, and while stirring, 18.3 g of dimethoxymethylsilane was slowly added dropwise.
  • ⁇ Viscosity measurement method of mixture of polyoxyalkylene polymers (A) and (B)> Weigh out a total of 15 g of polyoxyalkylene polymers (A) and (B) into a 100 mL cup so that they have a predetermined weight ratio, and use a spatula to add 2. The mixture was thoroughly mixed by hand at room temperature for a minute. Thereafter, the mixture was transferred to a 20 mL screw bottle and left to stand at room temperature for 20 hours to remove bubbles.
  • each curable composition was filled into a moisture-proof cartridge-type container to produce each curable composition.
  • various test specimens were prepared and evaluated in a constant temperature and humidity atmosphere of 23° C. and 50% relative humidity.
  • Al A1050P board (manufactured by Nihon Takuto Co., Ltd.)

Landscapes

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

Abstract

La présente invention concerne un mélange de polymères à base de polyoxyalkylène qui contiennent des groupes silyle hydrolysables et avec lesquels une accumulation de force d'adhérence est améliorée. L'invention concerne spécifiquement un mélange de polymères à base de polyoxyalkylène (A) et (B), les structures terminales des deux comprenant un groupe silyle hydrolysable ainsi qu'un groupe oléfine terminal et/ou un groupe oléfine interne. Le polymère (A) présente une structure de chaîne principale linéaire, ne comporte qu'une structure terminale dans chaque molécule et présente une masse moléculaire moyenne en nombre de 1000 à 8000. Le polymère (B) présente une structure de chaîne principale ramifiée et une masse moléculaire moyenne en nombre de 6000 à 15 000. Le nombre molaire du groupe silyle hydrolysable divisé par le nombre molaire total du groupe silyle hydrolysable, du groupe oléfine terminal et du groupe oléfine interne est d'au moins 0,50 et inférieur à 1,00 pour le polymère (A) et est d'au moins 0,60 et inférieur à 1,00 pour le polymère (B). Dans le mélange, le rapport pondéral du polymère (A) au polymère (B) est de 5:95 à 60:40.
PCT/JP2023/006849 2022-03-07 2023-02-24 Mélange de polymères à base de polyoxyalkylène et composition durcissable WO2023171425A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-034571 2022-03-07
JP2022034571 2022-03-07

Publications (1)

Publication Number Publication Date
WO2023171425A1 true WO2023171425A1 (fr) 2023-09-14

Family

ID=87935099

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/006849 WO2023171425A1 (fr) 2022-03-07 2023-02-24 Mélange de polymères à base de polyoxyalkylène et composition durcissable

Country Status (1)

Country Link
WO (1) WO2023171425A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005073322A1 (fr) * 2004-01-30 2005-08-11 Kaneka Corporation Composition durcissable
WO2018105704A1 (fr) * 2016-12-07 2018-06-14 株式会社カネカ Composition de résine liquide
WO2020066551A1 (fr) * 2018-09-26 2020-04-02 Ａｇｃ株式会社 Composition durcissable, produit durci et élément d'étanchéité
WO2022163562A1 (fr) * 2021-01-29 2022-08-04 株式会社カネカ Mélange de polymères de polyoxyalkylène et composition durcissable
JP2022135913A (ja) * 2021-03-03 2022-09-15 Ａｇｃ株式会社 硬化性組成物及びその硬化物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005073322A1 (fr) * 2004-01-30 2005-08-11 Kaneka Corporation Composition durcissable
WO2018105704A1 (fr) * 2016-12-07 2018-06-14 株式会社カネカ Composition de résine liquide
WO2020066551A1 (fr) * 2018-09-26 2020-04-02 Ａｇｃ株式会社 Composition durcissable, produit durci et élément d'étanchéité
WO2022163562A1 (fr) * 2021-01-29 2022-08-04 株式会社カネカ Mélange de polymères de polyoxyalkylène et composition durcissable
JP2022135913A (ja) * 2021-03-03 2022-09-15 Ａｇｃ株式会社 硬化性組成物及びその硬化物

Similar Documents

Publication Publication Date Title
JP6527589B2 (ja) 硬化性組成物
JP5744759B2 (ja) 硬化性組成物
JP6356123B2 (ja) 硬化性組成物
JP6682227B2 (ja) 硬化性組成物
JP7249998B2 (ja) 反応性ケイ素基含有重合体、および硬化性組成物
WO2015105122A1 (fr) Composition durcissable
WO2015080067A1 (fr) Composition durcissable
JP7073167B2 (ja) 硬化性組成物
JP2014234396A (ja) 室温硬化性組成物およびその硬化物
JP7285247B2 (ja) 反応性ケイ素基含有重合体、および硬化性組成物
CN116997610A (zh) 固化性组合物及其固化物
JP2024009271A (ja) ポリオキシアルキレン系重合体及び硬化性組成物
US20230027947A1 (en) Mixture of polyoxyalkylene polymers and curable composition
JPWO2016047519A1 (ja) 硬化性組成物およびその硬化物
WO2022181545A1 (fr) Procédé de fabrication d'un polymère comprenant un groupe silyle hydrolysable, et polymère, composition durcissable et produit durci
WO2018199270A1 (fr) Composition durcissable
JP6283509B2 (ja) 反応性ケイ素基含有重合体および硬化性組成物
WO2023171425A1 (fr) Mélange de polymères à base de polyoxyalkylène et composition durcissable
JP2021055013A (ja) 反応性ケイ素基含有重合体及び硬化性組成物
JP2021055017A (ja) 硬化性組成物
JP7469875B2 (ja) 硬化性組成物及びその硬化物
CN113795547B (zh) 固化性组合物及固化物
JP2023149911A (ja) 加水分解性シリル基含有ポリオキシアルキレン系重合体及びその製造方法、並びにその組成物
WO2023162664A1 (fr) Composition durcissable et son utilisation
WO2022202132A1 (fr) Composition contenant un polymère pouvant être réticulé par du silane

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23766603

Country of ref document: EP

Kind code of ref document: A1