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WO2018199270A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2018199270A1
WO2018199270A1 PCT/JP2018/017091 JP2018017091W WO2018199270A1 WO 2018199270 A1 WO2018199270 A1 WO 2018199270A1 JP 2018017091 W JP2018017091 W JP 2018017091W WO 2018199270 A1 WO2018199270 A1 WO 2018199270A1
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group
polymer
curable composition
mass
organic polymer
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Japanese (ja)
Inventor
章徳 佐藤
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Kaneka Corp
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Kaneka Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a curable composition containing an organic polymer having a reactive silicon group.
  • An organic polymer having at least one reactive silicon group in the molecule is crosslinked by forming a siloxane bond due to a hydrolysis reaction of the silicon group due to moisture or the like.
  • Such organic polymers are known to give rubbery cured products by the aforementioned crosslinking.
  • curable compositions using organic polymers having reactive silicon groups are widely used in applications such as sealing materials, adhesives and paints. These curable compositions are required to have curability, workability, stability, and the like depending on applications.
  • the obtained cured product is required to have various physical properties such as adhesiveness, flexibility, strength, hardness, restorability, and heat resistance.
  • the curable composition needs to exhibit the above physical properties in a well-balanced manner.
  • curable compositions are required to have fast curability and are used for various purposes. For this reason, in order to use the same curable composition for various uses, it is preferable that each physical property is exhibited simultaneously at a high level while exhibiting fast curability.
  • Patent Document 2 a curable composition containing an organic polymer having a specific reactive silicon group, an amine compound, and an acidic compound has been proposed (Patent Document 2).
  • the curable composition described in Patent Document 2 is excellent in surface fast curability, adhesiveness, restoration property, and storage stability.
  • the curable composition described in Patent Document 2 is particularly useful for adhesive applications.
  • a curable composition that provides a cured product that can be cured in a short time and can maintain good rubber elasticity over a long period of time has been proposed (Patent Document 3).
  • the above-mentioned curable compositions proposed in Patent Documents 1 to 3 exhibit other excellent physical properties while exhibiting rapid curability. However, depending on the application, a plurality of properties among many properties such as deep curability and storage stability of the curable composition and tear strength and heat resistance of the cured product may be required.
  • the effective compositions described in Patent Documents 1 to 3 still have room for improvement in that these characteristics can be exhibited simultaneously in the same composition.
  • the present inventors have solved the above problems with a curable composition containing an organic polymer having a specific reactive silicon group and a (meth) acrylic organic polymer having a specific structure.
  • the present inventors have found that the present invention can be accomplished and have completed the present invention.
  • R 1 represents a hydrogen atom on the first carbon atom in an aliphatic hydrocarbon group having one or more hydrogen atoms on the first carbon atom and having 1 to 20 carbon atoms.
  • An organic polymer (B) which is a (meth) acrylic organic polymer having a reactive silicon group represented by:
  • the curable composition whose ratio which the structural monomer unit derived from methyl methacrylate accounts for 20 mass% or more and 90 mass% or less among all the structural monomer units which comprise an organic polymer (B).
  • R 1 in the general formula (1) is a methoxymethyl group.
  • the blend ratio of the organic polymer (A) and the organic polymer (B) is 90:10 to 40:60 in terms of mass ratio (organic polymer (A): organic polymer (B)).
  • the blending ratio of the organic polymer (A) and the organic polymer (B) is 75:25 to 55:45 in terms of mass ratio (organic polymer (A): organic polymer (B)).
  • R 3 , R 5 , and R 6 are hydrogen atoms. atoms, or, carbon atoms a 1 to 20 substituted or unsubstituted hydrocarbon group, two R 5 and two R 6 may be the same, may be different .R 3 , R 4, two R 5, and a compound having an amidine structure or guanidine structure represented by any two or more ring structure by bonding with and may form.) of the two R 6
  • (19) The curable composition according to (17), wherein the organic tin compound (c2) is a dialkyltin compound.
  • (20) A cured product obtained by curing the curable composition according to any one of (1) to (19).
  • (21) A sealing material containing the curable composition according to any one of (1) to (19).
  • an organic polymer (A) having a reactive silicon group hereinafter also referred to as a polymer (A)
  • an organic polymer (B) hereinafter referred to as a (meth) acrylic organic polymer
  • the surface curability is good, and the cured product has elongation, tear strength, heat resistance, storage stability, deep curability, and adhesiveness. It is possible to provide a curable composition having an excellent balance, a cured product of the curable composition, and a sealing material and an adhesive containing the curable composition.
  • the polymer in the present specification conforms to the following definition.
  • a polymer contains all the polymer components obtained by the manufacturing process of the polymer, and includes components having different molecular weight, structure, number of substituents, and the like.
  • the average molecular weight, the molecular weight distribution, and the amount of substituents introduced on average per molecule are used.
  • representative molecular structures are sometimes described for convenience.
  • the organic polymer (A) has the following general formula (1) -SiR 1 a X 3-a (1)
  • R 1 represents a hydrogen atom on the first carbon atom in an aliphatic hydrocarbon group having one or more hydrogen atoms on the first carbon atom and having 1 to 20 carbon atoms.
  • X represents a hydroxyl group or a hydrolyzable group, a is 1 or 2, R 1 , And when there are a plurality of them, they may have the same or different reactive silicon groups.
  • substitution of at least one of the hydrogen atoms on the carbon atom at the 1-position with any of an oxygen atom, a nitrogen atom, and a sulfur atom is an oxygen atom, a nitrogen atom, or a sulfur atom. It includes not only substitution by atoms but also substitution by oxygen atom-containing groups, nitrogen atom-containing groups, or sulfur atom-containing groups.
  • R 1 when the hydrogen atom on the carbon atom at the 1-position is replaced by an oxygen atom-containing group, a nitrogen atom-containing group, or a sulfur atom-containing group, at least one oxygen atom in the oxygen atom-containing group, nitrogen At least one nitrogen atom in the atom-containing group or at least one sulfur atom in the sulfur atom-containing group is bonded to the carbon atom at the 1-position.
  • the aliphatic hydrocarbon group having one or more hydrogen atoms on the 1-position carbon atom constituting the main skeleton of R 1 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an ethynyl group.
  • Alkynyl and the like can be mentioned.
  • the group containing an oxygen atom, a nitrogen atom or a sulfur atom substituted on the carbon atom at the 1-position of R 1 in the general formula (1) is not particularly limited.
  • the oxygen atom-containing group include an oxo group ( ⁇ O), an alkoxy group, an alkenyloxy group, an aryloxy group, and an acyloxy group.
  • the nitrogen atom-containing group include an amino group, an alkylamino group, an alkylimino group, a carbamate group, and a ureido group.
  • S thioxo group
  • an oxygen atom-containing group, a nitrogen atom-containing group, and a sulfur atom-containing group are bonded to the 1-position carbon atom of R 1 , two of the plurality of groups are bonded to each other. To form a ring.
  • Examples of such a group include 2,5-dioxacyclopentyl group, 3-methyl-2,5-dioxacyclopentyl group, 1-methyl-2,5-dioxacyclopentyl group and the like.
  • the oxygen atom-containing group attached to the carbon atom at the 1-position of R 1, the nitrogen atom-containing group or a sulfur atom-containing group may be any of the carbon atoms in the aliphatic hydrocarbon group constituting the main skeleton of R 1 To form a ring.
  • Such a group includes a 2-oxacyclopentyl group.
  • R 1 in the general formula (1) include a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-propenoxymethyl group, a phenoxymethyl group, an acetoxymethyl group, a dimethoxymethyl group, a trimethoxymethyl group, Methoxymethyl group, 2-oxacyclopentyl group, 2,5-dioxacyclopentyl group, 3-methyl-2,5-dioxacyclopentyl group, 1-methyl-2,5-dioxacyclopentyl group, acetyl group, and methoxy A group in which at least one hydrogen atom on the carbon atom at the 1-position is substituted with an oxygen atom, such as a carbonyl group; an aminomethyl group, a 1-aminoethyl group, an N-methylaminomethyl group, an N, N-dimethylaminomethyl group; N-ethylaminomethyl group, N-phenyla
  • a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a phenoxymethyl group, and an acetoxy group are excellent in the balance between the high activity of the reactive silicon group and the storage stability of the curable composition. More preferred is a group in which one of the hydrogen atoms on the 1-position carbon atom is substituted with an oxygen atom, such as a methyl group.
  • a methoxymethyl group is particularly preferable in terms of excellent balance of physical properties of the cured product.
  • X in the general formula (1) represents a hydroxyl group or a hydrolyzable group.
  • the hydrolyzable group include known hydrolyzable groups. Specific examples of the hydrolyzable group include, for example, hydrogen, halogen, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, alkylthio group, An arylthio group, an alkylsulfonyloxy group, an arylsulfonyloxy group and the like can be mentioned. In these, a halogen, an alkoxy group, an alkenyloxy group, and an acyloxy group are preferable.
  • the reactive silicon group-containing polymer must be stable before reacting with the presence of water and a catalyst. For this reason, as a hydrolysable group, the alkoxy group with moderate hydrolyzability is more preferable.
  • a methoxy group and an ethoxy group are more preferable from the viewpoint of easy production of raw materials.
  • a methoxy group is particularly preferred from the standpoint of both activity and ease of handling.
  • an ethoxy group and an isopropenoxy group are preferable because ethanol and acetone, which are safe and easy to remove, are eliminated by hydrolysis.
  • the reactive silicon group represented by the general formula (1) include (methoxymethyl) dimethoxysilyl group, bis (methoxymethyl) methoxysilyl group, (methoxymethyl) diethoxysilyl group, and bis (methoxy Methyl) ethoxysilyl group, (ethoxymethyl) dimethoxysilyl group, bis (ethoxymethyl) methoxysilyl group, (1-methoxyethyl) dimethoxysilyl group, bis (1-methoxyethyl) methoxysilyl group, (phenoxymethyl) dimethoxysilyl Group, bis (phenoxymethyl) methoxysilyl group, (phenoxymethyl) diethoxysilyl group, bis (phenoxymethyl) ethoxysilyl group, (acetoxymethyl) dimethoxysilyl group, bis (acetoxymethyl) methoxysilyl group, (acetoxymethyl) Diethoxysilyl group, (Acetoxymethyl) ethoxys
  • the reactive silicon group represented by the general formula (1) is not limited to these. Of these, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, and (N, N-diethylaminomethyl) dimethoxysilyl group are preferable from the viewpoint of activity. A (methoxymethyl) dimethoxysilyl group is more preferable because the cured product exhibits good mechanical properties.
  • the polymer (A) may have other reactive silicon groups in addition to the group represented by the general formula (1).
  • specific examples of other reactive silicon groups include methyldimethoxysilyl group, methyldiethoxysilyl group, dimethylmethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, and (methoxymethyl) methylmethoxysilyl group. It is done.
  • the method for introducing a reactive silicon group into the polymer (A) is not particularly limited.
  • a reactive silicon group can be introduced into the polymer (A) using a known method.
  • the method (i) is preferable because the reaction is simple, the amount of the reactive silicon group introduced is adjusted, and the physical properties of the resulting reactive silicon group-containing polymer are stable.
  • the method (ii) is preferable because there are many reaction options and it is easy to increase the rate of introduction of reactive silicon groups.
  • the number of silicon groups introduced may be expressed as silicon group introduction rate or functionalization rate with respect to the number of reactive groups as described above in the polymer before introduction. It is natural that the number of silicon in the reactive silicon-based polymer is controlled by the silicon group introduction rate, but unreacted reactive groups may affect the physical properties of the polymer and the polymer-containing composition. is there. For example, the reactivity may change or the viscosity may change during long-term storage of the composition.
  • the silicon group introduction rate is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more.
  • the lower limit is preferably 1.1 or more, and the upper limit is preferably 5 or less.
  • the lower limit of the average number of reactive silicon groups per molecule is preferably 1.8 or more, and more preferably 2.0 or more.
  • the upper limit is more preferably 3.0 or less. If the average number of reactive silicon groups per molecule is too small, sufficient bonding between polymers is difficult to occur, and it is difficult to obtain a cured product having desired physical properties. On the other hand, if the average number of molecules per reactive silicon group is too large, the stretchability of the cured product may be lowered, and it is economically disadvantageous.
  • the lower limit of the average number of reactive silicon groups per molecule is preferably 1.2 or more, and 1.4 More preferably.
  • the average number of reactive silicon groups per molecule in the polymer (A) is determined by a method of quantifying protons on carbon directly bonded with reactive silicon groups by high resolution 1 H-NMR measurement.
  • the reactive silicon group may be present at either the molecular chain end, the side chain end, or both of the polymer (A).
  • the presence of a reactive silicon group having two hydroxyl groups and two hydrolyzable groups at the end of the molecular chain makes it easy to obtain a rubber-like cured product exhibiting high strength and high elongation due to the long molecular weight between crosslinking points.
  • the number average molecular weight of the polymer (A) is not particularly limited.
  • the number average molecular weight is preferably 3,000 or more and 100,000 or less, more preferably 3,000 or more and 50,000 or less, and particularly preferably 3,000 or more and 30,000 or less in terms of polystyrene in GPC. If the number average molecular weight is too small, the amount of reactive silicon groups introduced is large, which may be inconvenient in terms of production cost. When the number average molecular weight is excessive, the viscosity of the polymer (A) or the curable crude composition tends to be inconvenient in terms of workability.
  • polystyrene conversion molecular weight in GPC was measured using Tosoh HLC-8120GPC as a liquid feeding system, Tosoh TSK-GEL H type as a column, and tetrahydrofuran (THF) as a solvent. The same applies to other molecular weight notations in this specification.
  • the molecular weight distribution (Mw / Mn) of the polymer (A) is not particularly limited.
  • the molecular weight distribution is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less.
  • the main chain of the polymer (A) may be linear or may have a branched chain.
  • the main chain of the polymer (A) is preferably a straight chain from the viewpoint of obtaining a cured product exhibiting good elongation properties.
  • the number of branched chains of the main chain of the polymer (A) is 1 or more and 4 or less in order to maintain good elongation properties of the cured product. More preferably, it is most preferably 1.
  • the main chain skeleton of the organic polymer (A) is not particularly limited. Polymers having various main chain skeletons can be used as the organic polymer (A). For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyisobutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, polyoxypropylene-poly Polyoxyalkylene polymers such as oxyisobutylene copolymers, polyoxyethylene-polyoxytetramethylene copolymers, and polyoxypropylene-polyoxytetramethylene copolymers; ethylene-propylene copolymers, polyisobutylene, Copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymers of butadiene and acrylonitrile and / or styrene
  • Each of the above polymers may be mixed in a block shape, a graft shape or the like.
  • a polyether polymer such as a polyoxyalkylene polymer, a polyester polymer, or a polycarbonate polymer is used as a base polymer for an adhesive or a sealing material
  • an adhesive group having a low molecular weight component is used. It is preferable because there is little contamination due to transfer to materials.
  • polyoxyalkylene polymers are more preferred because they have high moisture permeability and are excellent in deep-part curability when made into a one-component composition, and are also excellent in adhesiveness.
  • Polyoxypropylene is particularly preferred as the main chain skeleton of the polyoxyalkylene polymer, since it is amorphous and has a relatively low glass transition temperature to give a cured product having low viscosity and excellent cold resistance.
  • the polymer (A) may be a polymer having any one of the main chain skeletons described above or a mixture of polymers having different main chain skeletons. Moreover, about a mixture, the mixture of the polymer each manufactured separately may be sufficient, and the mixture manufactured simultaneously so that it may become arbitrary mixed compositions may be sufficient.
  • the glass transition temperature of the polymer (A) is not particularly limited.
  • the glass transition temperature of the polymer (A) is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and particularly preferably ⁇ 20 ° C. or lower.
  • the glass transition temperature can be determined by DSC measurement according to the measurement method defined in JISK7121.
  • the polyoxyalkylene polymer is a polymer having a repeating unit represented by —R 7 —O— (wherein R 7 is a linear or branched alkylene group having 1 to 14 carbon atoms). Is preferred. R 7 is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.
  • Specific examples of the repeating unit represented by —R 7 —O— include —CH 2 O—, —CH 2 CH 2 O—, —CH 2 CH (CH 3 ) O—, —CH 2 CH (C 2 H 5 ) O—, —CH 2 C (CH 3 ) (CH 3 ) O—, —CH 2 CH 2 CH 2 CH 2 O— and the like.
  • the main chain structure of the polyoxyalkylene polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units.
  • those composed of a polyoxypropylene polymer having a repeating unit of oxypropylene of 50% by mass or more, preferably 80% by mass or more of the polymer main chain structure It is preferable from the point of being crystalline and having a relatively low viscosity.
  • the polyoxyalkylene polymer is preferably a polymer obtained by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator.
  • cyclic ether compound examples include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these cyclic ether compounds, propylene oxide is particularly preferable because an amorphous and relatively low viscosity polyether polymer can be obtained.
  • the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, And alcohols such as sorbitol; polyoxyalkylene polymers such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.
  • the number average molecular weight of the polyoxyalkylene polymer is preferably from 300 to 5,000.
  • Examples of the polymerization method of the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH; and a complex obtained by reacting an organoaluminum compound and porphyrin described in JP-A-61-215623.
  • Polymerization method using transition metal compound-porphyrin complex catalyst JP-B-46-27250, JP-B-59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3,427,334, And a polymerization method using a double metal cyanide complex catalyst shown in US Pat. No.
  • the main chain skeleton of the polymer (A) may contain bonds other than oxyalkylene bonds, such as urethane bonds, as long as the effects of the present invention are not significantly impaired.
  • the urethane bond is not particularly limited.
  • Examples of the urethane bond include a bond formed by a reaction between an isocyanate group and a group containing active hydrogen (hereinafter also referred to as an amide segment).
  • the amide segment is not particularly limited.
  • Examples of the amide segment include a urethane bond formed by a reaction between an isocyanate group and a hydroxyl group; a urea bond formed by a reaction between an isocyanate group and an amino group; a thiourethane bond formed by a reaction between an isocyanate group and a mercapto group, and the like. Examples thereof include a bond having an amide bond, and a bond formed by further reacting an active hydrogen in the aforementioned urethane bond, urea bond, and thiourethane bond with an isocyanate group.
  • a cured product obtained by curing a curable composition comprising a polymer containing a urethane bond or an ester bond in the main chain may be cleaved at the urethane bond or ester bond portion by heat or the like.
  • the strength of the cured product may be significantly reduced depending on the curing conditions of the cured product.
  • the viscosity of the polymer tends to be high. Moreover, a viscosity may rise after storage, and workability
  • the average number of amide segments per molecule is preferably 1 or more and 10 or less, more preferably 1.5 or more and 5 or less.
  • the number of 1 to 3 is particularly preferable. When the number is less than 1, the curability may not be sufficient. When the number is more than 10, the polymer may have a high viscosity and may be difficult to handle.
  • Organic polymer (B) which is a reactive silicon group-containing (meth) acrylic organic polymer
  • the organic polymer (B) has the following general formula (2): -SiR 2 a X 3-a (2)
  • R 2 is an unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
  • X and a are the same as those in the general formula (1).
  • R 2 in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, and a cyclohexyl group.
  • Alkyl groups such as 2-ethylhexyl group and n-dodecyl group; unsaturated hydrocarbon groups such as vinyl group, isopropenyl group and allyl group; aromatic carbon groups such as phenyl group, toluyl group and 1-naphthyl group A hydrogen group etc. are mentioned.
  • a methyl group and a phenyl group are preferable from the viewpoint of the balance between the activity of the reactive silicon group and the physical properties of the cured product.
  • a methyl group is more preferable in view of availability of raw materials.
  • X in the general formula (2) represents a hydroxyl group or a hydrolyzable group, and can be explained in the same manner as X in the general formula (1).
  • a 1 or 2.
  • a 1 or 2.
  • the reactive silicon group represented by the general formula (2) examples include a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, an ethyldiethoxysilyl group, an n-propyldimethoxysilyl group, Examples include n-hexyldimethoxysilyl group, phenyldimethoxysilyl group, phenyldiethoxysilyl group, methyldiisopropenoxysilyl group, methyldiphenoxysilyl group, methyldimethoxysilyl group, and dimethylmethoxysilyl group.
  • the reactive silicon group represented by the general formula (2) is not limited to these. Among these, a methyldimethoxysilyl group is preferable from the viewpoint that the activity and cured product exhibit a good balance of physical properties.
  • the polymer (B) may have other reactive silicon groups in addition to the group represented by the general formula (2).
  • specific examples of other reactive silicon groups include a trimethoxysilyl group, a triethoxysilyl group, and a (methoxymethyl) methylmethoxysilyl group.
  • the proportion of the constituent monomer units derived from methyl methacrylate in the constituent monomer units is 20 mass percent or more and 90 mass percent or less. If there is no particular limitation. It is preferable to use 1 type and / or 2 or more types of monomer (b) which has (meth) acrylic structures other than methyl methacrylate.
  • the constituent monomer means only a compound having a carbon-carbon double bond in the molecule and polymerizing the carbon-carbon double bond to constitute the polymer (B).
  • the proportion of the constituent monomer units derived from methyl methacrylate in the constituent monomer units constituting the main chain structure of the polymer (B) is 20 mass percent or more and 90 mass percent or less.
  • the proportion is preferably 30 mass percent or more and 85 mass percent or less, and more preferably 50 mass percent or more and 80 mass percent or less. If the proportion of the constituent monomer units derived from methyl methacrylate in the constituent monomer units is too small, the strength of the cured product may be reduced. If it is too large, the reactive silicon group content of the polymer (B) may be included. There exists a tendency for compatibility with an organic polymer (A) to fall.
  • the monomer (b) having a (meth) acrylic structure other than methyl methacrylate include methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, neopentyl (meth) acrylate, n-heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid alkyl ester monomers such as lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, (meth ) 3-
  • the monomer (b1) containing a reactive silicon group represented by the general formula (2) includes 3- (methyldimethoxysilyl) propyl (meth) acrylate, 3-methacrylic acid 3- (Methyldiethoxysilyl) propyl, 2- (methyldimethoxysilyl) ethyl (meth) acrylate, and (methyldimethoxysilyl) methyl (meth) acrylate.
  • 3- (methyldimethoxysilyl) propyl methacrylate is preferred because it is easily available.
  • 3- (trimethoxysilyl) propyl (meth) acrylate As the monomer (b2) containing a reactive silicon group not represented by the general formula (2), 3- (trimethoxysilyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, ( Examples include 2- (trimethoxysilyl) ethyl (meth) acrylate, trimethoxysilylmethyl (meth) acrylate, and triethoxysilylmethyl (meth) acrylate. Of these, 3- (trimethoxysilyl) propyl methacrylate is preferred because it is easily available. These may be used alone or in combination of two or more together with methyl methacrylate.
  • the polymer (B) contains a constituent monomer unit derived from one or more monomers having an alkyl group having 10 to 30 carbon atoms. Preferably, it contains a constituent monomer unit derived from stearyl methacrylate. Examples of the monomer having an alkyl group having 10 to 30 carbon atoms include lauryl (meth) acrylate, hexadecyl (meth) acrylate, and stearyl (meth) acrylate. Further, the total amount of the constituent monomer units derived from the aforementioned monomer having an alkyl group having 10 to 30 carbon atoms in the polymer (B) is 1 mass relative to the total mass of the constituent monomer units. % To less than 50% by mass is preferable, and 10% to 30% by mass is more preferable.
  • monomers exhibiting copolymerizability with these may be used as long as the physical properties are not impaired.
  • monomers include styrene monomers such as styrene, vinyl toluene, ⁇ -methyl styrene, chlorostyrene, and styrene sulfonic acid; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
  • Maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl ester, and maleic acid dialkyl ester; fumaric acid and its derivatives, such as fumaric acid, fumaric acid monoalkyl ester, and fumaric acid dialkyl ester; maleimide , Methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide And maleimide monomers such as cyclohexylmaleimide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; olefin monomers such as ethylene and propylene; butadiene and isoprene, etc.
  • maleimide Methylmaleimide, e
  • Conjugated diene monomers (meth) acrylonitrile; vinyl monomers such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether, and butyl vinyl ether. These may be used alone or in combination of two or more.
  • the monomer units constituting the main chain structure of the polymer (B) include methyl methacrylate and (meth) acrylic acid alkyl esters.
  • the content of the monomer is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • (meth) acrylic acid butyl and (meth) acrylic acid alkyl ester monomer having an alkyl group having 7 to 9 carbon atoms or (meth) acrylic acid alkyl ester having an alkyl group having 10 to 30 carbon atoms Combined use with monomers and combined use of (meth) acrylic acid alkyl ester monomers having 1 or 2 carbon atoms and (meth) acrylic acid alkyl ester monomers having 7 to 9 carbon atoms Is preferable from the viewpoint of compatibility between the organic polymer (A) and the organic polymer (B).
  • the method for synthesizing the acrylic polymer (B) is not particularly limited, and may be a known method.
  • a radical polymerization method is preferred from the viewpoint of versatility of monomers and ease of control of the polymerization reaction.
  • Radical polymerization methods can be broadly divided into “free radical polymerization methods” and “living radical polymerization methods”.
  • the “free radical polymerization method” is a method for polymerizing monomers using an azo compound, a peroxide or the like as a polymerization initiator, and is a simple polymerization method. According to the “free radical polymerization method”, it is possible to obtain a polymer having a functional group at the terminal by using a chain transfer agent having a specific functional group.
  • the “living radical polymerization method” the polymer growth terminal grows without causing a side reaction such as a termination reaction under specific reaction conditions.
  • a method for obtaining an acrylic polymer using a metallocene catalyst as disclosed in JP-A-2001-040037 and a thiol compound having at least one reactive silicon group in the molecule a vinyl monomer as shown in JP-A-57-502171, JP-A-59-006207, and JP-A-60-511992 is used in a stirred tank reactor. It is also possible to use a high temperature continuous polymerization method in which continuous polymerization is performed.
  • the method for introducing a reactive silicon group into the (meth) acrylic acid ester polymer is not particularly limited.
  • the following method can be used.
  • (Iii) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive silicon-containing group together with the above-described monomer. When this method is used, reactive silicon groups tend to be randomly introduced into the main chain of the polymer.
  • (Iv) A method of polymerizing a (meth) acrylate polymer using a mercaptosilane compound having a reactive silicon-containing group as a chain transfer agent. When this method is used, a reactive silicon group can be introduced into the polymer terminal.
  • V A compound having a polymerizable unsaturated group and a reactive functional group (V group) is copolymerized, and then the V group of the obtained copolymer reacts with the reactive silicon group and the V group.
  • a method of reacting a compound having a functional group Specifically, after copolymerizing 2-hydroxyethyl acrylate, a method of reacting a hydroxyl group of the obtained copolymer with an isocyanate silane having a reactive silicon-containing group, or copolymerizing glycidyl acrylate Then, the method etc. with which the epoxy group which the obtained copolymer has, and the aminosilane compound which has a reactive silicon containing group can be illustrated.
  • (Vi) A method of introducing a reactive silicon group by modifying a terminal functional group of a (meth) acrylic acid ester polymer synthesized by a living radical polymerization method.
  • the (meth) acrylic acid ester polymer obtained by the living radical polymerization method is easy to introduce a functional group at the polymer terminal.
  • a reactive silicon group can be introduced into the polymer terminal.
  • Examples of the silicon compound that can be used to introduce the reactive silicon group of the (meth) acrylic acid ester-based polymer using the above method include the following compounds.
  • Examples of the compound having a polymerizable unsaturated group and a reactive silicon group used in the method (iii) include (meth) acrylic acid (methyldimethoxysilyl) methyl, (meth) acrylic acid (methyldiethoxysilyl) methyl, Examples include 2- (methyldimethoxysilyl) ethyl (meth) acrylate and 3- (methyldimethoxysilyl) propyl (meth) acrylate. From the viewpoint of availability, 3- (methyldimethoxysilyl) propyl methacrylate is preferable.
  • Mercaptosilane compounds having reactive silicon-containing groups used in method (iv) include (mercaptomethyl) methyldimethoxysilane, (3-mercaptopropyl) methyldimethoxysilane, (mercaptomethyl) methyldiethoxysilane, and ( And 3-mercaptopropyl) methyldiethoxysilane.
  • (3-mercaptopropyl) methyldimethoxysilane is particularly preferable.
  • Examples of the compound having a reactive silicon group and a functional group that reacts with the V group used in the method (v) include (isocyanate methyl) methyldimethoxysilane, (isocyanatemethyl) methyldiethoxysilane, and (3-isocyanatepropyl).
  • Isocyanate silane compounds such as methyldimethoxysilane and (3-isocyanatopropyl) methyldiethoxysilane; (glycidoxymethyl) methyldimethoxysilane, (glycidoxymethyl) methyldiethoxysilane, (3-glycidoxypropyl) Epoxysilane compounds such as methyldimethoxysilane and (3-glycidoxypropyl) methyldimethoxysilane; (aminomethyl) methyldimethoxysilane, (N-cyclohexylaminomethyl) methyldimethoxysilane, (N-phenyl) Aminomethyl) methyldimethoxysilane, and the like (N-(2-aminoethyl) aminomethyl) aminosilane compounds such as methyl dimethoxy silane.
  • any denaturation reaction can be used.
  • a polymer using a compound having a functional group capable of reacting with a terminal reactive group obtained by polymerization and a compound having a silicon group, or a compound having a functional group capable of reacting with a terminal reactive group and a double bond can be used.
  • a method in which a double bond is introduced at the terminal and a reactive silicon group is introduced into the double bond at the polymer terminal by hydrosilylation or the like can be used.
  • the above-mentioned isocyanate silane can be used.
  • Hydrosilanes used for hydrosilylation include (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) diethoxysilane, (ethoxymethyl) dimethoxysilane, (amino Methyl) dimethoxysilane, (dimethylaminomethyl) dimethoxysilane, (diethylaminomethyl) dimethoxysilane, (N- (2-aminoethyl) aminomethyl) dimethoxysilane, (acetoxymethyl) dimethoxysilane, and (acetoxymethyl) diethoxysilane And hydrosilanes. If the method (vi) is used, a reactive silicon group-containing (meth) acrylate polymer having a narrow molecular weight distribution can be obtained by arbitrarily controlling the molecular weight.
  • a reactive silicon group can be introduced into both the molecular chain terminal and / or the side chain.
  • the number average molecular weight of the (meth) acrylic acid ester polymer is not particularly limited, but is preferably a molecular weight in terms of polystyrene by GPC measurement, preferably 500 or more and 15,000 or less, more preferably 500 or more and 10,000 or less, and 1,000 or more. 4,000 or less is particularly preferable.
  • the number average molecular weight of the (meth) acrylic acid ester polymer is within the above range, it is easy to form a cured product exhibiting sufficient rubber elasticity, and there is an advantageous tendency in terms of workability with respect to viscosity.
  • the number average molecular weight is in the range of 1,000 to 4,000, the balance between physical properties and viscosity of the cured product tends to be particularly excellent.
  • the reactive silicon group of the reactive silicon group-containing (meth) acrylic acid ester polymer may be introduced at either the molecular chain terminal or the main chain.
  • a polymer in which a reactive silicon group is introduced only at the end of the molecular chain is used, the elongation characteristics of the resulting cured product tend to be improved.
  • the adhesiveness of the curable composition may be improved.
  • the average number of reactive silicon groups per molecule is preferably 0.5 or more and 4.0 or less, more preferably 0.7 or more and 3.5 or less, and 1.0 or more and 3.0. The following are particularly preferred:
  • the blending ratio of the polymer (A) and the polymer (B) is not particularly limited.
  • the mass ratio (polymer (A): polymer (B)) is preferably 90:10 to 40:60, more preferably 75:25 to 55:45.
  • the blending ratio of the polymer (B) is small, the cured product may not exhibit sufficient heat resistance.
  • the blending ratio of the polymer (B) is large, the flexibility of the cured product tends to decrease.
  • Specific examples of the combination of the reactive silicon group represented by the general formula (1) and the reactive silicon group represented by the general formula (2) include (methoxymethyl) dimethoxysilyl group, methyldimethoxysilyl group, Combinations of (methoxymethyl) diethoxysilyl and methyldimethoxysilyl, (ethoxymethyl) dimethoxysilyl and methyldimethoxysilyl, and (methoxymethyl) dimethoxysilyl and methyldiethoxysilyl And a combination of an (alkoxymethyl) dialkoxysilyl group and an alkyldialkoxy group.
  • a combination of a (methoxymethyl) dimethoxysilyl group and a methyldimethoxysilyl group is preferable because the balance between the curability of the curable composition and the physical properties of the cured product is good.
  • an amine compound (c1) and / or an organic tin compound (c2) can be used as the condensation catalyst (C).
  • the condensation catalyst (C) promotes a crosslinking reaction by hydrolysis / condensation between reactive silicon groups of the polymer (A) and the polymer (B).
  • amine compound (c1) examples include aliphatic primary amines; aliphatic secondary amines; aliphatic tertiary amines; aliphatic unsaturated amines; aromatic amines; nitrogen-containing heterocyclic compounds.
  • a compound having an amidine structure or a guanidine structure represented by the following general formula (3) can be particularly preferably used.
  • R 3 N CR 4 -NR 5 2 (3)
  • R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group represented by —NR 6 2.
  • R 3 , R 5 , and R 6 are: A hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and two R 5 and two R 6 may be the same or different. Any two or more of 3 , R 4 , two R 5 , and two R 6 may be bonded to form a cyclic structure.
  • the compound having the amidine structure or guanidine structure represented by the general formula (3) include 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU), 6- (dibutylamino). ) -1,8-diazabicyclo [5,4,0] undec-7-ene (DBA-DBU), 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,4,0] undec-7- Ene (OH-DBU), a compound in which the hydroxyl group of OH-DBU is modified by urethanation or the like, and a compound having an amidine structure such as 1,5-diazabicyclo [4,3,0] non-5-ene (DBN); DBU phenol salt (specifically, trade name: U-CAT SA1 (manufactured by SANAPRO)), DBU octylate (specifically, trade name: U-CAT SA102 (SANAPRO) DBU p-toluenesulfonate (specific
  • DBU, DBA-DBU, DBN, and phenylguanidine are preferable because of high activity, and DBU and phenylguanidine are more preferable.
  • amine compound (c1) examples include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecyl.
  • Aliphatic primary amines such as amine, cetylamine, stearylamine, and cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine , Didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, and buty Aliphatic secondary amines such as stearylamine; Aliphatic tertiary amines such as triethylamine, diisopropylethylamine, tributylamine, trihexylamine, and trioctylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine Aromatic amines such as aniline, lauryl aniline, steary
  • the total number of carbon atoms of the amine compound (c1) is preferably 2 or more, and more preferably 6 or more.
  • the amine compound (c1) is liquid in terms of easy handling and preparation of the composition.
  • the amine compound (c1) is in a solid state in that bleeding out can be suppressed.
  • the amine compound (c1) may be used by dissolving or dispersing in a liquid compound as necessary.
  • a liquid compound which can be used From the viewpoint of the VOC reduction
  • liquid compounds with low volatility include N-ethyltoluenesulfonamide, N-butylbenzenesulfonamide (BBSA), tetrahydrothiophene-1,1-dioxide (sulfolane), 2-pyrrolidone, N-methyl- Examples include 2-pyrrolidone, polyoxyalkylene, and alkyl ethers thereof.
  • the usage-amount of a liquid compound has the preferable range of 20 to 500 mass parts with respect to 100 mass parts of amine compounds (c1).
  • amine compounds (c1) may be used alone or in combination of two or more.
  • the amount of the amine compound (c1) used is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B). 05 parts by mass or more and 5 parts by mass or less are more preferable, and 0.1 parts by mass or more and 1 part by mass or less are particularly preferable. If the amount of the amine compound (c1) used is too small, the curing rate may become insufficient, or the curing reaction may not proceed sufficiently. On the other hand, if the amount used is too large, the curing speed is too high, and the usable time of the curable composition tends to be short, resulting in poor workability and poor storage stability.
  • a compound that forms a salt with the amine compound (c1) may be used.
  • any one or more of phenols, organic sulfonic acids, and inorganic acids may be used. Specific examples include phenol and phenol derivatives; organic sulfonic acids such as trifluoromethanesulfonic acid and p-toluenesulfonic acid; and inorganic acids such as hydrochloric acid, phosphoric acid, and boronic acid.
  • the amount of the compound that forms a salt with the amine compound (c1) is 0.001 part by mass or more and 20 parts by mass with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B). Or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 5 parts by mass or less. If the amount used is too small, the effect of suppressing bleeding out of the amine compound (c1) may be insufficient. On the other hand, if the amount used is excessive, the curing rate tends to be slow.
  • organic tin compound (c2) examples include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis ( Ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dibutyl tin dimethoxide , Dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis (acety
  • dioctyltin compounds are preferred because they exhibit moderate activity.
  • dioctyltin diacetylacetonate and dioctyltin dilaurate are more preferable.
  • organotin compounds (c2) may be used alone or in combination of two or more.
  • the organic tin compound (c2) When the organic tin compound (c2) is used, the elongation of the cured product tends to be improved as compared with the case where the amine compound (c1) is used. On the other hand, when the amine compound (c1) is used, the resilience of the cured product tends to be improved.
  • the amount of the organic tin compound (c2) used is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B). 0.05 parts by mass or more and 5 parts by mass or less is more preferable, and 0.1 parts by mass or more and 1 part by mass or less are particularly preferable. If the amount of the organic tin compound (c2) used is too small, the curing rate may be insufficient, or the curing reaction may not proceed sufficiently. On the other hand, if the amount used is too large, the curing speed is too high, and therefore the time that the curable composition can be used tends to be short, resulting in poor workability and poor storage stability.
  • the amine compound (c1) and the organotin compound (c2) may be used alone or in combination.
  • the ratio of the amount used in combination is not particularly limited as long as the effects of the invention are not impaired.
  • the curable composition contains the amine as a condensation catalyst (C).
  • an acidic compound (c3) may be used in combination.
  • the acidic compound (c3) is selected from Lewis acid or carboxylic acid.
  • the addition of the acidic compound (c3) tends to improve the storage stability of the curable composition and the tear strength of the cured product.
  • the Lewis acid as the acidic compound (c3) is not particularly limited.
  • Specific examples of Lewis acids include triethoxyborane, triethoxyaluminum, triisopropoxyaluminum, isopropoxyaluminum bis (ethylacetoacetate), diisopropoxyaluminum (ethylacetoacetate), tetraethoxytitanium, tetraisopropoxytitanium, Tetrabutoxytitanium, diisopropoxytitanium bisacetylacetonate, diisopropoxytitanium bis (ethylacetoacetate), tetrabutoxyzirconium, butoxyzirconium (acetylacetonato) bis (ethylacetoacetate), tetrabutoxyhafnium, tetraethoxygermanium, pentaethoxy Alkoxy metals such as tantalum and pentaethoxyniobium; boron trifluoride dieth
  • titanium compounds such as alkoxy titanium are preferable in terms of availability, handling properties, and catalytic activity.
  • titanium compounds when used in combination, only one of the titanium compounds may be used, or two or more may be used in combination.
  • carboxylic acid of an acidic compound (c3) there is no restriction
  • Preferred examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-diethyl.
  • Examples include butyric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, and versatic acid.
  • the amount of the acidic compound (c3) used is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the polymer (A). More preferably, it is 1 to 5 parts by mass.
  • condensation catalyst (C) other condensation catalysts other than the amine compound (c1), the organic tin compound (c2), and the acidic compound (c3) can be used.
  • condensation catalysts include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3- (N-2-aminoethylamino) propyltrimethoxysilane.
  • Aminosilanes such as: tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, carboxyl Carboxylic acid metal salts such as iron acid, cobalt carboxylate, nickel carboxylate, and cerium carboxylate; organic acidic phosphate ester; organic sulfonic acid such as trifluoromethanesulfonic acid; inorganic such as hydrochloric acid, phosphoric acid, and boronic acid ; Ammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, cesium fluoride, ammonium bifluoride, Na 2 SiF 6, K 2 SiF 6, and (NH 4) fluorine-anion-containing compounds such as 2 SiF 6 and Can be mentioned.
  • a photoacid generator or a photobase generator that generates an acid or a base by light can also be used as a condensation catalyst.
  • the amount of the condensation catalyst other than the amine compound (c1), the organic tin compound (c2), and the acidic compound (c3) is 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B). 0.001 to 10 parts by mass is preferable, 0.01 to 7 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.
  • the curable composition contains the polymer (A) and the polymer (B) as essential components.
  • the curable composition does not have the reactive silicon group represented by the general formula (1) in addition to the polymer (A) and the polymer (B) as necessary, and the general formula (3): -SiR 2 3-a X a (3)
  • An organic polymer (D) other than the (meth) acrylic organic polymer having a reactive silicon group represented by the formula (wherein R 2 , X and a are the same as described above) may be included.
  • R 2 , X and a are the same as described above.
  • the reactive silicon group represented by the general formula (3) is not particularly limited.
  • Examples of the reactive silicon group represented by the general formula (3) include a methyldimethoxysilyl group, a methyldiethoxysilyl group, a methyldiisopropoxysilyl group, a methyldiisopropenyloxysilyl group, a methoxydimethylsilyl group, and An ethoxydimethylsilyl group etc. are mentioned.
  • a methyldimethoxysilyl group is preferable from the viewpoints of curability and mechanical properties of the obtained cured product.
  • the main chain skeleton of the polymer (D) and the synthesis method thereof can be explained in the same manner as the polymer (A).
  • the polymer (D) can be used by mixing at an arbitrary ratio with respect to the total of the polymer (A) and the polymer (B).
  • the ratio of the mixture can be selected from the viewpoint of curing speed, stability, cost, and the like.
  • the mixing ratio of the polymer (D) to the total of 100 parts by mass of the mass of the polymer (A) and the mass of the polymer (B) is preferably from 0 to 100 parts by mass, and from 0 to 50 parts by mass. The following is more preferable, and 0 to 20 parts by mass is further preferable.
  • the mixing ratio of the polymer (D) is 100 parts by mass or more, the curability of the composition may be lowered.
  • the polymer (A) and the polymer (D) may be of the same type or different types with respect to the main chain skeleton, but are preferably compatible with each other.
  • the polymer (A) may contain a reactive silicon-containing group represented by the general formula (3) in the molecule.
  • polysiloxane can be used to the extent that the effects of the invention are not impaired.
  • Polysiloxane is a polymer whose main chain is composed of repeating siloxane bonds.
  • examples of the polysiloxane include polydimethylsiloxane.
  • the polysiloxane those showing fluidity at room temperature can be used.
  • the main chain may contain other polymer components such as polyoxyalkylene.
  • the strength of the cured product may be improved.
  • the blending amount of the polysiloxane is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 to 50 parts by mass with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B). Particularly preferred is 10 to 30 parts by mass.
  • a plasticizer (E) can be added to the curable composition.
  • a plasticizer By adding a plasticizer, the viscosity of the curable composition and the mechanical properties such as hardness, tensile strength, and elongation of the cured product obtained by curing the curable composition can be adjusted. On the other hand, the tear strength of the cured product tends to decrease due to the addition of the plasticizer.
  • plasticizer (E) examples include phthalic acid ester compounds such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and butyl benzyl phthalate; Terephthalic acid ester compounds such as (2-ethylhexyl) -1,4-benzenedicarboxylate; non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, Aliphatic polycarboxylic acid ester compounds such as diisodecyl succinate and tributyl acetyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyl ricin
  • a polymer plasticizer can be used.
  • the polymer plasticizer include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol having a number average molecular weight of 500 or more, and polypropylene glycol, hydroxy groups of these polyether polyols as ester groups, and And / or polyethers such as derivatives converted to ether groups; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene.
  • polymer plasticizers those compatible with the mixture of the polymer (A) and the polymer (B) are preferable.
  • phthalic acid ester compounds non-phthalic acid ester compounds, polyethers and vinyl polymers are preferred.
  • the amount of the plasticizer used is preferably 100 parts by mass or less, more preferably 20 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B).
  • the following are particularly preferred: When the amount of the plasticizer used is too large, the mechanical strength of the cured product tends to be insufficient.
  • a plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.
  • a solvent or a diluent can be added to the curable composition.
  • the solvent and diluent are not particularly limited.
  • As the solvent and diluent aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether and the like can be used.
  • the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and 250 ° C. or higher under atmospheric pressure because of the problem of air pollution when the composition is used indoors. C. or higher is particularly preferable.
  • the said solvent or diluent may be used independently and may be used together 2 or more types.
  • An adhesiveness imparting agent can be added to the curable composition.
  • an adhesiveness imparting agent a silane coupling agent or a reaction product of a silane coupling agent can be added.
  • silane coupling agent examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and (2-aminoethyl) aminomethyltrimethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyl Isocyanate group-containing silanes such as triethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatemethyltrimethoxysilane, and ⁇ -isocyanatemethyldimethoxymethyl
  • the above-mentioned adhesion imparting agent may be used alone or in combination of two or more.
  • the reaction material of various silane coupling agents can also be used.
  • the amount of the silane coupling agent to be used is preferably 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass with respect to 100 parts by mass as the total of the mass of the polymer (A) and the polymer (B). Part is particularly preferred.
  • Fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, Examples thereof include carbon black, ferric oxide, aluminum fine powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber and filament.
  • the amount of the filler used is preferably 1 to 300 parts by mass, particularly preferably 10 to 250 parts by mass with respect to a total of 100 parts by mass of the mass of the polymer (A) and the polymer (B).
  • an organic balloon or an inorganic balloon may be added to the curable composition.
  • the balloon is a spherical filler with a hollow inside.
  • the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran.
  • the amount of the balloon used is that of the polymer (A).
  • the amount is preferably from 0.1 to 100 parts by weight, particularly preferably from 1 to 20 parts by weight, based on 100 parts by weight in total of the weight and the weight of the polymer (B).
  • an anti-sagging agent may be added to the curable composition as needed to prevent sagging and improve workability.
  • the sagging inhibitor is not particularly limited. Examples of the sagging inhibitor include 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 the sagging inhibitor used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B).
  • antioxidant antioxidant agent
  • the weather resistance of the cured product can be increased.
  • examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.
  • the amount of the antioxidant used is preferably 0.1 to 10 parts by weight, and preferably 0.2 to 5 parts by weight with respect to 100 parts by weight as the total of the weight of the polymer (A) and the weight of the polymer (B). Is particularly preferred.
  • a light stabilizer can be used.
  • Use of a light stabilizer can prevent photooxidation degradation of the cured product.
  • Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds.
  • a hindered amine system is particularly preferable.
  • the light stabilizer is preferably used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight in total of the weight of the polymer (A) and the weight of the polymer (B). Is particularly preferred.
  • an ultraviolet absorber can be used.
  • the surface weather resistance of the cured product can be enhanced.
  • ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds.
  • a benzotriazole type is particularly preferable.
  • commercially available products include Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (above, manufactured by BASF).
  • the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by mass, and preferably 0.2 to 5 parts by mass with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B). Is particularly preferred.
  • the physical property modifier which adjusts the tensile characteristic of the hardened
  • the physical property modifier include alkyl alkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; aryl such as diphenyldimethoxysilane and phenyltrimethoxysilane Alkoxysilanes; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and ⁇ -glycidoxypropylmethyldiisopropenoxysilane; tris (trimethylsilyl) borate, and tris (triethylsilyl) ) Trialkylsilyl borates such
  • the physical property adjusting agent By using the physical property adjusting agent, it is possible to increase the hardness when the curable composition is cured, or conversely to decrease the hardness and to bring about elongation at break.
  • the said physical property modifier may be used independently and may be used together 2 or more types.
  • a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product.
  • Particularly preferred are compounds that produce trimethylsilanol.
  • Compounds that generate monovalent silanol groups in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol. Mention may be made of silicon compounds that produce monools.
  • the amount of the physical property modifier used is preferably 0.1 to 10 parts by mass, and preferably 0.5 to 5 parts by mass with respect to 100 parts by mass as a total of the mass of the polymer (A) and the polymer (B). Is particularly preferred.
  • a tackifying resin can be added to the curable composition for the purpose of improving the adhesion and adhesion to the substrate, or as necessary.
  • tackifying resin a commonly used resin can be used.
  • tackifying resins include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone indenes.
  • Resin Resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, styrene block copolymer, hydrogenated styrene block copolymer, petroleum Examples thereof include resins (for example, C5 hydrocarbon resins, C9 hydrocarbon resins, C5 hydrocarbon-C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, and DCPD resins. These may be used alone or in combination of two or more.
  • the amount of the tackifying resin used is preferably 2 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass or more and 50 parts by mass with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B).
  • the following is more preferable, and 5 parts by mass or more and 30 parts by mass or less is more preferable.
  • the amount is less than 2 parts by mass, it is difficult to obtain adhesion and adhesion effects to the substrate.
  • the amount exceeds 100 parts by mass the viscosity of the curable composition becomes too high, and handling of the curable composition may be difficult. .
  • a compound having an epoxy group can be used.
  • the restorability of the cured product can be improved.
  • the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof.
  • the amount of the compound having an epoxy group is preferably in the range of 0.5 to 50 parts by mass with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B).
  • a photocurable material can be used in the curable composition.
  • 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 such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound.
  • Typical photocurable materials include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, polyvinyl cinnamates or azido resins. Can be used.
  • the amount of the photocurable substance used is preferably 0.1 parts by mass or more and 20 parts by mass or less, with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B), 0.5 mass More preferred is 10 parts by mass or more. If the amount used is too small, it is difficult to obtain the effect of increasing the weather resistance of the cured product to the desired extent. If the amount used is excessive, the cured product tends to be cracked because the cured product is too hard.
  • an oxygen curable substance can be used.
  • the oxygen curable substance include unsaturated compounds that can react with oxygen in the air.
  • the oxygen curable substance reacts with oxygen in the air to form a cured film in the vicinity of the surface of the cured product, and has an effect of preventing stickiness of the surface and adhesion of dust and dust to the surface of the cured product.
  • Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers, epoxy resins, and silicon resins.
  • Modified products with drying oil 1,2-polybutadiene, 1,4-polybutadiene, and C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene
  • diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene
  • liquid polymers such as polymers. These may be used alone or in combination of two or more.
  • the amount of the oxygen curable substance used is preferably 0.1 parts by mass or more and 20 parts by mass or less, with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B), and 0.5 mass. More preferred is 10 parts by mass or more. If the amount used is less than 0.1 parts by mass, the improvement in contamination may not be sufficient. If the amount used exceeds 20 parts by mass, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.
  • An epoxy resin can be added to the curable composition.
  • a composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles.
  • the epoxy resin include bisphenol A type epoxy resins and novolac type epoxy resins.
  • the use ratio of these epoxy resins and the total of the polymer (A) and the polymer (B) is 100/1 as (polymer (A) + polymer (B)) / epoxy resin in mass ratio.
  • a range of ⁇ 1 / 100 is preferred.
  • the mass ratio is within the above range as (polymer (A) + polymer (B)) / epoxy resin, it is easy to obtain the effect of improving the impact strength and toughness of the cured product, and the cured product has good strength. Easy to form.
  • a curing agent for curing the epoxy resin can be added to the curable composition together with the epoxy resin.
  • the amount used is in the range of 0.1 to 300 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • the curable composition can be prepared as a one-component curable composition in which all the components are pre-mixed and stored in a sealed state.
  • the one-component curable composition is cured at room temperature after application by moisture in the air.
  • the curable composition comprises a compounding material as a curing agent in which components such as a curing catalyst, a filler, a plasticizer, and water are blended, and an organic polymer composition mixed with the compounding material before use. It can also be prepared as a two-component curable composition. From the viewpoint of workability, a one-component curable composition is preferable.
  • the curable composition is of a one-component type
  • all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred.
  • n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, and ⁇ -glycidoxypropyltri By adding a silicon compound that can react with water, such as methoxysilane, the storage stability is further improved.
  • the amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1% with respect to 100 parts by mass in total of the mass of the polymer (A) and the mass of the polymer (B). It is preferably no less than 20 parts by mass and no greater than 0.5 parts by mass and no greater than 10 parts by mass.
  • the method for preparing the curable composition is not particularly limited.
  • normal ingredients such as blending the above ingredients and kneading them at room temperature or under heat using a mixer, roll, kneader, etc. or using a small amount of a suitable solvent to dissolve and mix the ingredients are adopted. Can be done.
  • the curable composition has a good curing rate, deep curability, and storage stability, and gives a cured product having an excellent balance of tear strength and heat resistance.
  • curable properties such as adjusting the curing rate and controlling the physical properties of the resulting cured product by arbitrarily mixing and using the composition containing no polymer (A) and polymer (B).
  • the use of a composition is also possible.
  • the curable composition is a moisture reaction type composition in which the reaction proceeds with moisture.
  • the curable composition can also be used as a so-called dual curable composition that is used in combination with a thermosetting resin, a photocurable resin, or a radiation curable resin.
  • curable resins using reactions such as ene-thiol addition reaction, (meth) acrylic radical polymerization reaction, epoxy group ring-opening polymerization reaction, hydrosilylation addition reaction, and urethanization reaction are used in combination. can do.
  • Curable compositions are adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, waterproofing coating materials, mold preparations, antivibration materials, vibration damping materials, soundproofing materials, foam materials Can be used for paint, spraying material, etc.
  • a cured product obtained by curing the curable composition is excellent in flexibility and adhesiveness. For this reason, it is more preferable that the curable composition is used as a sealing material or an adhesive among them.
  • electrical and electronic component materials such as solar cell backside sealing materials; electrical and electronic components such as insulation coating materials for electric wires and cables; and electrical insulating materials for electrical and electronic devices; potting agents for electrical and electronic; acoustic insulation Materials: Adhesives such as elastic adhesives, contact adhesives, tile adhesives, adhesives for asphalt waterproofing materials, and adhesives for temporary fixings; spray type sealing materials; crack repair materials; powder paints; Materials; Medical rubber materials, medical adhesives, medical adhesive sheets, medical equipment sealing materials, medical / dental materials such as dental impression materials, or processed materials for medical / dental products; food packaging materials ; Sealing materials for joints of exterior materials such as sizing boards; Coating materials; Anti-slip coating materials; Buffer materials; Primers; Conductive materials for shielding electromagnetic waves; Thermally conductive materials; Hot melt materials; Gasket; Concrete reinforcing material; Various molding materials; Sealing material for rust prevention and waterproofing of meshed glass and laminated glass end face (cut part); Automobile parts such as ordinary passenger cars, large vehicle
  • the above-mentioned curable composition can be used for a wide variety of applications such as adhesive mounting of plastic covers, trims, flanges, bumpers, window mountings, interior members, and exterior parts. Furthermore, the cured product of the curable composition of the previous operation can be adhered to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings alone or in the presence of a primer. For this reason, the above-mentioned curable composition can also be used as various types of sealing compositions and adhesive compositions.
  • the curable composition is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, an adhesive for wall finishing, Adhesives for vehicle panels, adhesives for electrical, electronic and precision equipment assembly, leather, textiles, adhesives for bonding fabrics, paper, boards and rubber, reactive post-crosslinking pressure sensitive adhesives, direct glazing sealing Materials, sealing materials for double glazing, sealing materials for SSG construction or building working joints, sealing materials used for applications other than those described above, civil engineering adhesives or sealing materials, and bridge adhesives or sealing materials Can also be used. Furthermore, it can be used as an adhesive material such as an adhesive tape or an adhesive sheet.
  • Polyoxypropylene (A-5) of straight-chain branched mixture having an average of 1.8 silicon groups, a number average molecular weight of 20,000 and Mw / Mn 1.37 and having a (chloromethyl) dimethoxysilyl group at the terminal Got.
  • each polymer was mixed with a filler and a (plasticizer) sagging inhibitor and kneaded thoroughly, and then dispersed through three paint rolls. Thereafter, dehydration under reduced pressure at 120 ° C. for 2 hours using a planetary mixer, cooling to 50 ° C. or lower, adding a dehydrating agent, an adhesion-imparting agent, and a condensation catalyst (C), with substantially no moisture present Kneaded. After degassing under reduced pressure, it was sealed in a cartridge which is a moisture-proof container to obtain a one-component curable composition. After storing the cartridge type container at 23 ° C. for 1 week and / or at 50 ° C. for 4 weeks, various test specimens were prepared in a constant temperature and humidity atmosphere at 23 ° C. and 50% relative humidity, and various evaluations were performed.
  • each of the constituent polymers is shown for easy comparison even in Examples and Comparative Examples using the polymer (AB) as the polymer.
  • the polymer actually used for preparing the composition is shown in the row of “polymer used” in each table.
  • the curable composition is filled into a 5 mm thick mold using a spatula, the surface is touched with a spatula, and the time until the composition does not adhere to the spatula is peeled.
  • the curing time was measured as the tension time (before storage at 50 ° C.).
  • the time for which the surface was flattened was defined as the curing start time.
  • the curable composition was stored at 50 ° C. for 28 days, then placed at 23 ° C. for 1 hour or longer, and the skinning time was measured in the same manner as described above (after storage at 50 ° C.). Moreover, the rate of change of the skinning time after storage relative to the skinning time before storage was determined.
  • the curable composition was BM type viscometer manufactured by Tokyo Keiki Co., Ltd., rotor no. 7 was used to measure the 2 rpm viscosity (before storage at 50 ° C.).
  • the curable composition was stored at 50 ° C. for 28 days and then placed at 23 ° C. for 1 hour or longer. Moreover, the change rate of the viscosity after storage with respect to the viscosity before storage was calculated
  • the curable composition was filled in a polyethylene tube having a diameter of 12 mm without bubbles, and scraped with a spatula so that the surface was horizontal to prepare a test specimen. did. After leaving the specimen at 23 ° C. and 50% relative humidity for 3 days or 7 days, turn off the cured part of the surface layer, remove the uncured part cleanly, and then measure the thickness of the cured part using calipers. did.
  • the curable composition was filled into a sheet-like mold having a thickness of 3 mm. After curing for 3 days at 23 ° C. and 50% relative humidity, curing was performed for 4 days in a 50 ° C. dryer to obtain a sheet-like cured product. The obtained cured product was punched into a No. 3 dumbbell type or No. 7 dumbbell type according to JIS K 6251 to obtain a test piece. Using the obtained test piece, a tensile test (tensile speed: 200 mm / min) is performed using an autograph at 23 ° C.
  • dumbbell prepared in the same manner was stored in a 90 ° C. dryer for 28 days, then in a 120 ° C. dryer for 14 days, and then placed at 23 ° C. for 1 hour or longer, and a tensile test was performed in the same manner as described above ( After storage at 90 ° C. + 120 ° C.).
  • the curable composition was filled into a sheet-like mold having a thickness of 3 mm. After curing for 3 days at 23 ° C. and 50% relative humidity, curing was performed for 4 days in a 50 ° C. dryer to obtain a sheet-like cured product. The obtained cured product was punched into a tear test dumbbell mold (JIS A type) to obtain a test piece. Using the obtained test piece, a tear test (tensile speed: 200 mm / min) was performed using an autograph at 23 ° C. and a relative humidity of 50%, and the stress at break was measured.
  • JIS A type tear test dumbbell mold
  • the sheet-like cured product was punched out into a No. 7 dumbbell type to obtain a dumbbell type test piece.
  • a 10 mm marked line was drawn on the constricted portion of the dumbbell-shaped test piece.
  • the dumbbell-shaped test piece was fixed in a stretched state so that the distance between the marked lines was 15 mm, and left standing in a 70 ° C. dryer. After 24 hours, the fixation was released, and the restoration rate was determined by measuring the marked line after 3 hours and 24 hours at 23 ° C. and 50% relative humidity.
  • the curable composition was applied at 23 ° C. and 50% relative humidity so as to be in close contact with various substrates. The applied curable composition was then cured for 7 days at 23 ° C. and 50% relative humidity. The obtained cured product was subjected to a 90 ° hand peel test, and the adhesiveness was evaluated based on the cohesive failure rate of the adhesive interface.
  • the evaluation criteria are as follows. A: 95% or more B: 50% or more and less than 95% C: 5% or more and less than 50% and strong resistance at peeling D: Less than 5% and strong resistance at peeling E: 5% or more 50 Less than% and resistance at peeling is weak F: Less than 5% and resistance at peeling is weak
  • the curable composition containing a combination of the polymer (A) and the polymer (B) has a good balance of physical properties, compared to the case where a polymer substituted with chlorine atoms is used instead of the polymer (A), It turns out that it is excellent in storage stability and adhesiveness.
  • the curable composition containing a combination of the polymer (A) and the polymer (B) has a good balance of physical properties, and has a reactive silicon group represented by the general formula (2) instead of the polymer (B). It can be seen that the deep part curability, the elongation, the heat resistance, and the tear strength are excellent as compared with the case of using a polymer that does not have.
  • the curable composition containing the polymer (A) and the polymer (B) in combination has a good balance of physical properties, and the elongation, heat resistance, tear strength, and adhesion are better than when the polymer (B) is not used. It turns out that it is excellent in property.
  • the curable composition comprising a combination of the polymer (A) and the polymer (B) has a good balance of physical properties, and the proportion of methyl methacrylate in the constituent monomer units instead of the polymer (B).
  • the elongation, heat resistance, tear strength, and adhesiveness are excellent compared to the case where the (meth) acrylic polymer having a MMA content of less than 20 mass percent is used.
  • the curable composition containing a combination of the polymer (A) and the polymer (B) has a good balance of physical properties, and when the polymer (D) is further added, the general formula is used instead of the polymer (B).
  • the polymer which does not have the reactive silicon group represented by (2) it turns out that it is excellent in deep part sclerosis
  • the curable composition containing a combination of the polymer (A) and the polymer (B) has a good balance of physical properties, and has a reactive silicon group represented by the general formula (2) instead of the polymer (B). It can be seen that the deep part curability, the elongation, the heat resistance, and the tear strength are excellent as compared with the case of using a polymer that does not have.
  • the curable composition containing the combination of the polymer (A) and the polymer (B) has a fast surface curability and the elongation, tear strength, heat resistance, storage stability of the cured product, It turns out that a favorable balance is shown regarding deep part curability and adhesiveness.

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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)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne une composition durcissable qui présente une bonne aptitude au durcissement de surface et fournit un produit durci qui présente un excellent équilibre entre allongement, résistance à la déchirure, résistance à la chaleur, stabilité au stockage, aptitude au durcissement dans une partie profonde et adhésivité; un produit durci qui est obtenu par durcissement de cette composition durcissable; et un matériau d'étanchéité et un adhésif, chacun contenant cette composition durcissable. Le problème précité peut être résolu à l'aide d'une composition durcissable qui contient un polymère organique (A) qui possède un groupe silicium réactif hautement actif spécifique et un polymère organique (B) qui est un polymère organique méthacrylique qui comporte une certaine quantité d'une unité méthacrylate de méthyle dans un composant monomère constitutif.
PCT/JP2018/017091 2017-04-26 2018-04-26 Composition durcissable Ceased WO2018199270A1 (fr)

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EP4583162A1 (fr) * 2022-08-31 2025-07-09 Mitsui Mining & Smelting Co., Ltd. Composition de fixation temporaire, procédé de fabrication de structure liée et utilisation d'une composition de fixation temporaire

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WO2012020560A1 (fr) * 2010-08-10 2012-02-16 株式会社カネカ Composition polymérisable
WO2012036109A1 (fr) * 2010-09-14 2012-03-22 株式会社カネカ Composition durcissable
JP2012057150A (ja) * 2010-08-10 2012-03-22 Kaneka Corp 硬化性組成物
JP2012214755A (ja) * 2011-03-31 2012-11-08 Kaneka Corp 硬化性組成物
JP2015205984A (ja) * 2014-04-18 2015-11-19 積水フーラー株式会社 硬化性組成物
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JP2010111870A (ja) * 2008-11-07 2010-05-20 Kaneka Corp 硬化性組成物および複層ガラス用シーリング材
WO2012020560A1 (fr) * 2010-08-10 2012-02-16 株式会社カネカ Composition polymérisable
JP2012057150A (ja) * 2010-08-10 2012-03-22 Kaneka Corp 硬化性組成物
WO2012036109A1 (fr) * 2010-09-14 2012-03-22 株式会社カネカ Composition durcissable
JP2012214755A (ja) * 2011-03-31 2012-11-08 Kaneka Corp 硬化性組成物
JP2015205984A (ja) * 2014-04-18 2015-11-19 積水フーラー株式会社 硬化性組成物
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JP7356247B2 (ja) 2019-03-28 2023-10-04 株式会社カネカ 硬化性組成物、及び硬化物

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