WO2014017218A1 - Composition durcissable à deux composants - Google Patents

Composition durcissable à deux composants Download PDF

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WO2014017218A1
WO2014017218A1 PCT/JP2013/066650 JP2013066650W WO2014017218A1 WO 2014017218 A1 WO2014017218 A1 WO 2014017218A1 JP 2013066650 W JP2013066650 W JP 2013066650W WO 2014017218 A1 WO2014017218 A1 WO 2014017218A1
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group
curable composition
meth
polymer
mass
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PCT/JP2013/066650
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Japanese (ja)
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慎吾 矢野
祐輔 岡部
齋藤　敦
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セメダイン株式会社
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Priority to JP2014526818A priority Critical patent/JP6198180B2/ja
Publication of WO2014017218A1 publication Critical patent/WO2014017218A1/fr

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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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds

Definitions

  • the present invention relates to a two-component curable composition and a cured product obtained by curing the curable composition.
  • a curable composition containing a crosslinkable silicon group-containing organic polymer has already been industrially produced and widely used in applications such as sealing materials, adhesives, and paints. Usually, these curable compositions are cured using various metal catalysts, and are used for various applications depending on the type and amount of addition.
  • a reaction product of organotin and an ester compound is conventionally known (see, for example, Patent Documents 1 to 4).
  • ester compounds in particular, a catalyst using a phthalate ester is generally used.
  • This phthalate ester is stipulated as a VOC guideline formulation substance by the Ministry of Health, Labor and Welfare, and its existence has been pointed out.
  • catalyst design with non-phthalate esters has been demanded.
  • a method using a dioctyltin compound instead of a dibutyltin compound has been proposed, but the dioctyltin compound has a problem that the reactivity is low and the curing rate is slow.
  • Patent Document 5 discloses (A) a reactive silicon group-containing polyoxyalkylene polymer and (B) an alkyl acrylate monomer unit and / or methacryl having substantially one or more molecular chains. (C) 1 to 60 parts by weight of a curing agent for epoxy resin with respect to 100 parts by weight of a component obtained by mixing a polymer comprising an acid alkyl ester monomer unit at a mass ratio of 100/0 to 1/99, D) 0.1 to 20 parts by weight of silane coupling agent and (E) A agent containing 0.1 to 5 parts by weight of water, (F) 10 to 80 parts by weight of epoxy resin, and (G) condensation catalyst Disclosed is a two-component curable composition comprising 0.1 to 8 parts by weight of a B agent.
  • (G) bis (dibutyltin laurate oxide) is used as a condensation catalyst.
  • Dibutyltin oxa The reaction product of de dialkyl phthalate, or an example of using dibutyltin bisacetylacetonate are described.
  • the curable composition described in Patent Document 5 uses a dibutyltin compound, there is a problem in safety, and since water is included as an essential component, storage stability may be lowered, and after storage There was a problem that the adhesive force may be reduced.
  • the present invention has been made in view of the above-described problems of the prior art, and the present invention is a two-component curable composition that has high safety, can accelerate the curing speed, and has excellent storage stability. And a cured product obtained by curing the curable composition.
  • the present inventors have conducted extensive research. As a result, by using a reaction product obtained by reacting a specific dioctyltin compound and a specific alkoxysilane compound, the safety is high and the curing rate is high. It was found that a two-component curable composition having a fast curing property and an excellent storage stability can be obtained.
  • the two-component curable composition of the present invention comprises an agent A containing an epoxy resin and a liquid tin-based curing catalyst, and an agent B containing a crosslinkable silicon group-containing organic polymer and an epoxy resin curing agent.
  • a liquid curable composition wherein the liquid tin-based curing catalyst is one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxy represented by the following formula (1):
  • a reaction product obtained by reacting with a silane compound, and the amount of the epoxy resin is 10 to 200 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer.
  • the blending amount is 0.1 to 20 parts by mass, and the blending amount of the epoxy resin curing agent is 1 to 60 parts by mass.
  • R 1 is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group or an epoxycycloalkyl group, preferably a phenyl group or a vinyl group, more preferably a phenyl group.
  • R 2 is a methyl group or a phenyl group.
  • a is 0 or 1 (provided that when R 1 is an alkyl group having 6 to 20 carbon atoms, a is 0)
  • R 3 is a monovalent hydrocarbon group having 1 to 4 carbon atoms and a monovalent halogen atom.
  • a plurality of R 3 groups may be the same or different.
  • the alkoxysilane compound is diphenyl dialkoxysilane.
  • the (A) crosslinkable silicon group-containing organic polymer is a polyoxyalkylene polymer having a crosslinkable silicon group, a (meth) acrylic polymer having a crosslinkable silicon group, and a saturated hydrocarbon having a crosslinkable silicon group. It is preferable that it is 1 or more types selected from the group which consists of a system polymer.
  • the cured product of the present invention is obtained by curing the two-component curable composition of the present invention.
  • security can be accelerated
  • curing this curable composition are provided. be able to.
  • the curable composition excellent in adhesiveness can be obtained.
  • the two-component curable composition of the present invention is a two-component type comprising an agent A containing an epoxy resin and a liquid tin-based curing catalyst, and an agent B containing a crosslinkable silicon group-containing organic polymer and an epoxy resin curing agent.
  • a curable composition, wherein the liquid tin-based curing catalyst is one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the formula (1)
  • the amount of the epoxy resin is 10 to 200 parts by mass and the amount of the liquid tin-based curing catalyst is 100 parts by mass of the crosslinkable silicon group-containing organic polymer. Is 0.1 to 20 parts by mass, and the amount of the epoxy resin curing agent is 1 to 60 parts by mass.
  • epoxy resin conventionally known ones can be widely used, and there is no particular limitation.
  • bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin and these are hydrogenated.
  • epoxy resins bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxies from the balance of workability, curability, adhesive strength, adherend versatility, water resistance, durability, etc.
  • Resin bisphenol S-type epoxy resin, epoxy resin hydrogenated with these, aliphatic epoxy resin, novolac-type epoxy resin, urethane-modified epoxy resin having urethane bond, fluorinated epoxy resin, rubber-modified epoxy resin, tetrabromobisphenol A Flame retardant epoxy resins such as glycidyl ether are preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, epoxy resins hydrogenated with these, novolac type epoxy resin , Urethane-modified epoxy resins having urethane bond, a rubber-modified epoxy resin is more preferable.
  • the molecular weight of the epoxy resin is not particularly limited, but the number average molecular weight is preferably 300 to 1000, more preferably 350 to 600.
  • the blending ratio of the epoxy resin is such that the blending amount of the epoxy resin is 10 to 200 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. Mass parts are preferred, and 50 to 120 parts by mass are more preferred.
  • the liquid tin-based curing catalyst is a reaction product obtained by reacting at least one tin compound selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate with an alkoxysilane compound represented by the following formula (1). It is a thing.
  • R 1 is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, or an epoxycycloalkyl group, which improves the stability of the liquid tin-based curing catalyst. Therefore, a phenyl group, a vinyl group, or an alkyl group having 6 to 20 carbon atoms is preferable, a phenyl group or a vinyl group is more preferable, and a phenyl group is particularly preferable.
  • R 2 is a methyl group or a phenyl group, and it is more preferable that R 1 and R 2 are both phenyl groups because the curing rate can be increased.
  • a is 0 or 1 (provided that a is 0 when R 1 is an alkyl group having 6 to 20 carbon atoms).
  • R 3 is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 4 carbon atoms and a monovalent halogenated hydrocarbon group, preferably a methyl group or an ethyl group, and a plurality of R 3 are the same It can be different.
  • alkoxysilane compound examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyl.
  • Epoxy group-containing silanes such as trimethoxysilane; vinyl group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylisopropoxysilane; hexyltrimethoxysilane, hexyltriethoxysilane, decyltri Alkylsilanes having an alkyl group having 6 to 20 carbon atoms such as methoxysilane; phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenylmethyldimethoxysilane, diphenyl Examples thereof include phenyl group-containing silanes such as methoxysilane and diphenyldiethoxysilane.
  • Phenyl group-containing silanes, vinyl group-containing silanes and alkylsilanes having an alkyl group having 6 to 20 carbon atoms are preferable, and phenyl group-containing silanes are preferable.
  • Silanes and vinyl group-containing silanes are more preferable, and diphenyl dialkoxysilane is particularly preferable in terms of curing speed.
  • dioctyl tin carboxylate a known dioctyl tin carboxylate can be used, and there is no particular limitation, but a dioctyl tin carboxylate having a structure represented by the following formula (2) is preferable.
  • n is 1 to 4, and R 11 and R 12 are each a monovalent organic group.
  • R 11 and R 12 are each a monovalent organic group.
  • an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a cycloalkenyl group, a cyclo An alkynyl group, an aryl group, an aralkyl group, etc. are mentioned, An alkyl group or an alkenyl group is preferable.
  • the carbon number of R 11 and R 12 is not particularly limited, but is preferably 1 to 21, more preferably 1 to 17, and still more preferably 1 to 11.
  • the dioctyltin carboxylate may be a commercially available dioctyltin carboxylate, or obtained by reacting dioctyltin oxide with at least one organic acid selected from the group consisting of monocarboxylic acids and monocarboxylic anhydrides.
  • the reaction product obtained may be used.
  • dioctyl tin oxide, an organic acid, and an alkoxysilane compound represented by the formula (1) may be added simultaneously to obtain a reaction product that is a liquid tin-based curing catalyst of the present invention.
  • a saturated carboxylic acid and / or an unsaturated carboxylic acid can be used, but a saturated fatty acid having 2 to 22 carbon atoms, an unsaturated fatty acid having 2 to 22 carbon atoms, and an aroma having 7 to 22 carbon atoms.
  • a group carboxylic acid or naphthenic acid is preferable, and a saturated fatty acid having 2 to 22 carbon atoms is particularly preferable.
  • a saturated carboxylic acid anhydride and / or an unsaturated carboxylic acid anhydride can be used, but a saturated fatty acid anhydride having 2 to 22 carbon atoms and an unsaturated carbon acid having 2 to 22 carbon atoms can be used. Saturated fatty acid anhydrides and aromatic carboxylic acid anhydrides having 7 to 22 carbon atoms are preferred.
  • the reaction conditions of one or more tin compounds selected from the group consisting of the dioctyl tin oxide and dioctyl tin carboxylate and the alkoxysilane compound represented by the following formula (1) are not particularly limited. It is preferred that the tin atom of the tin compound is reacted in the range of 0.20 to 1.40 mol, preferably 0.25 to 1.10. With respect to 1 mol of OR 3 groups of the alkoxysilane compound. If it is less than 0.20 mol, there is a possibility that a sufficient curing rate cannot be obtained under room temperature conditions and low temperature conditions. Further, sufficient deep part curability may not be obtained.
  • the rubber hardness of the resulting cured product tends to increase, and the elongation of the film of the cured product tends to decrease, such being undesirable.
  • it exceeds 1.40 mol it becomes difficult to dissolve the dioctyltin oxide and the alkoxysilane compound, and even if dissolved, the stability of the liquid tin-based curing catalyst tends to decrease.
  • this curing catalyst is used in a curable composition, the compatibility with the polymer (A) tends to decrease particularly under low temperature conditions, and a sufficient curing rate may not be obtained under low temperature conditions. Therefore, it is not preferable.
  • the temperature condition of the reaction is not particularly limited, but it is preferably heated at 70 to 140 ° C., more preferably 80 to 120 ° C.
  • the reaction rate can be increased by setting the reaction temperature to 70 ° C. or higher.
  • reaction temperature 140 degrees C or less side reactions, such as thermal decomposition and gelatinization, can be prevented.
  • the reaction time is not particularly limited, but is preferably 1 hour to 5 hours, and more preferably 1 hour to 3 hours. By this reaction, a liquid tin-based curing catalyst that is liquid at normal temperature (for example, 23 ° C.) can be obtained.
  • the reaction between the tin compound and the alkoxysilane compound may be performed by reacting one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate with an alkoxysilane compound, and dioctyltin.
  • An oxide, an organic acid, and an alkoxysilane compound may be reacted.
  • the carboxylic acid ester by-produced in the reaction between dioctyltin carboxylate and the alkoxysilane compound may or may not be removed, but is preferably used after being removed. By removing the by-produced carboxylic acid ester, the curing rate of the curable composition using the liquid tin-based curing catalyst of the present invention can be further increased.
  • the liquid tin-based curing catalyst may further contain other compounding substances such as a diluent and a plasticizer, and particularly preferably contains a diluent.
  • a diluent there is no particular limitation on the timing of adding other compounding substances such as a diluent, and it may be before or after the reaction between the tin compound and the alkoxysilane compound, but it is preferable to add the diluent before or during the reaction.
  • the diluent a diluent described later is preferably used.
  • the alkoxysilane compound may be used alone or in combination of two or more.
  • the blending ratio of the liquid tin-based curing catalyst is such that the blending amount of the liquid tin-based curing catalyst is 0.1 to 20 with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. Parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 8 parts by mass.
  • crosslinkable silicon group-containing organic polymer those having various main chain skeletons can be used, and on average, one molecule has 0.8 or more crosslinkable silicon groups and is mainly composed.
  • Organic polymers whose chain is not polysiloxane are preferred.
  • polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc.
  • Copolymer ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene
  • saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers can be obtained with a relatively low glass transition temperature.
  • the cured product is preferable because it is excellent in cold resistance.
  • Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their high moisture permeability and excellent deep-part curability when made into one-component compositions.
  • the crosslinkable silicon group of the (A) organic polymer used in the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond.
  • a group represented by the following general formula (3) is preferable.
  • R 21 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R 21 3 represents a triorganosiloxy group represented by SiO— (R 21 is the same as above), and when two or more R 21 are present, they may be the same or different.
  • X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different.
  • d represents 0, 1, 2, or 3, and e represents 0, 1, or 2, respectively.
  • p in the following general formula (4) need not be the same. p represents an integer of 0 to 19. However, d + (sum of e) ⁇ 1 is satisfied.
  • the hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and d + (sum of e) is preferably in the range of 1 to 5.
  • d + (sum of e) is preferably in the range of 1 to 5.
  • two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.
  • the number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.
  • crosslinkable silicon group a crosslinkable silicon group represented by the following general formula (5) is preferable because it is easily available.
  • R 21 and X are the same as those described above, and d is an integer of 1, 2 or 3.
  • d is preferably 2 or more, more preferably 3.
  • R 21 examples include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, and R 21 3 SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.
  • the hydrolyzable group represented by X is not particularly limited as long as it is a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxyl 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.
  • a hydrogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxyl group, an amide group, and an aminooxy group are more preferable.
  • An alkoxyl group is particularly preferred from the viewpoint of mild hydrolysis and easy handling.
  • alkoxyl groups those having fewer carbon atoms have higher reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group.
  • a methoxy group or an ethoxy group is usually used.
  • crosslinkable silicon group examples include trialkoxysilyl groups [—Si (OR) 3 ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. And a silyl group [—SiR 21 (OR) 2 ].
  • R is an alkyl group such as a methyl group or an ethyl group.
  • crosslinkable silicon group may be used alone or in combination of two or more.
  • the crosslinkable silicon group can be present in the main chain, the side chain, or both.
  • the number of silicon atoms forming the crosslinkable silicon group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less.
  • the organic polymer having a crosslinkable silicon group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000. Particularly preferred is 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.
  • the average number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more in one molecule of the polymer. 1.1 to 5 may be present. If the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability becomes insufficient and it becomes difficult to develop good rubber elastic behavior.
  • the crosslinkable silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends.
  • the crosslinkable silicon group is only at the end of the main chain of the molecular chain, so that the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.
  • the polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the following general formula (6). -R 22 -O- (6)
  • R 22 is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. .
  • repeating unit represented by the general formula (6) examples include -CH 2 O -, - CH 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H5) O -, - CH 2 C (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 O- Etc.
  • the main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
  • a polymer comprising a propylene oxide polymer as a main component is preferable because it is amorphous or has a relatively low viscosity.
  • a method for synthesizing a polyoxyalkylene polymer for example, a polymerization method using an alkali catalyst such as KOH, for example, organic aluminum as disclosed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623
  • KOH alkali catalyst
  • organic aluminum for example, organic aluminum as disclosed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623
  • a polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting a compound with a porphyrin for example, a polymerization method using a double metal cyanide complex catalyst shown in JP-B-46-27250 and JP-B-59-15336
  • a polyoxyalkylene system having a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less and a narrow molecular weight distribution according to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst A polymer can be obtained.
  • the main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component.
  • a urethane bond component examples include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; The thing obtained from reaction with coalescence can be mention
  • the introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule.
  • the reaction can be carried out by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter referred to as a polymer reaction method).
  • a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group
  • the method of obtaining the polyoxyalkylene type polymer which has this can be mention
  • An unsaturated group-containing polyoxyalkylene polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group, A polyoxyalkylene-based polymer having can be obtained.
  • polymer reaction method examples include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at a terminal.
  • examples thereof include a method of reacting a polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group.
  • an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.
  • polyoxyalkylene polymer having a crosslinkable silicon group examples include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767.
  • No. 57-164123 Japanese Patent Publication No. 3-2450, Japanese Patent Application Laid-Open No. 2005-213446, No. 2005-306891, International Publication No. WO 2007-040143, US Pat. No. 3,632,557, No. 4,345,053,
  • the ones proposed in the publications such as 4,960,844 can be listed.
  • the above polyoxyalkylene polymers having a crosslinkable silicon group may be used alone or in combination of two or more.
  • the saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc.
  • Diene compounds such as butadiene and isoprene are homopolymerized or copolymerized with the above olefin compounds. After that, it can be obtained by a method such as hydrogenation.
  • isobutylene polymers and hydrogenated polybutadiene polymers are easy to introduce functional groups at the terminals, control the molecular weight, and the number of terminal functional groups. Therefore, an isobutylene polymer is particularly preferable.
  • Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.
  • all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. Those containing at least mass% are preferred, those containing at least 80 mass% are more preferred, and those containing from 90 to 99 mass% are particularly preferred.
  • Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-62-254149, JP-A-62-2904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.
  • the above saturated hydrocarbon polymer having a crosslinkable silicon group may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer is not particularly limited, and various types can be used.
  • Alicyclic (meth) acrylic acid ester monomers phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, hydroxyethylated o-phenylphenol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxydiethyl Aromatic (meth) acrylic acid ester monomers such as ethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenylthioethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as 3-methoxybutyl, 2-hydroxyethyl (meth
  • the following vinyl monomers can be copolymerized together with the (meth) acrylic acid ester monomer.
  • the vinyl monomers include styrene monomers such as styrene, vinyl toluene, ⁇ -methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
  • Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl Maleimide monomers such as maleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and prop
  • the polymer which consists of a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferably, it is a (meth) acrylic acid ester-based polymer using one or two or more (meth) acrylic acid alkyl ester monomers and optionally using other (meth) acrylic acid monomers, By using the group-containing (meth) acrylic acid ester monomer together, the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled.
  • a methacrylic acid ester polymer composed of a methacrylic acid ester monomer is particularly preferred because of its good adhesiveness.
  • (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
  • the method for obtaining the (meth) acrylic acid ester polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037). Synthesis method described in JP-A-2003-313397), radical polymerization method using radical polymerization reaction is preferable.
  • the radical polymerization method a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator or a reactive silyl group is introduced at a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned.
  • a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a controlled radical polymerization method.
  • Examples of the controlled radical polymerization method include free radical polymerization method and living radical polymerization method using a chain transfer agent having a specific functional group, such as an addition-cleavage transfer reaction (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable.
  • a reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound Japanese Patent Laid-Open No. 2001-40037 are also suitable.
  • the above (meth) acrylic acid ester-based polymer having a crosslinkable silicon group may be used alone or in combination of two or more.
  • organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, it comprises a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group.
  • An organic polymer obtained by blending two or more selected from the group can also be used.
  • a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group is disclosed in JP-A-59-122541.
  • Japanese Laid-Open Patent Publication No. 63-112642 Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763
  • the invention is not particularly limited thereto.
  • Preferable specific examples include a crosslinkable silicon group and a molecular chain substantially having the following general formula (7): —CH 2 —C (R 25 ) (COOR 26 ) — (7) (Wherein R 25 represents a hydrogen atom or a methyl group, R 26 represents an alkyl group having 1 to 5 carbon atoms) and a monomer unit represented by the following general formula (8): —CH 2 —C (R 25 ) (COOR 27 ) — (8) (Wherein R 25 is the same as described above, and R 27 represents an alkyl group having 6 or more carbon atoms).
  • a copolymer comprising a (meth) acrylate monomer unit is represented by a crosslinkable silicon group. It is a method of blending and producing a polyoxyalkylene polymer.
  • R 26 in the general formula (7) is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group or the like, having 1 to 5 carbon atoms, preferably 1 to 4, more preferably 1 to 2 alkyl groups.
  • the alkyl group of R 26 may alone, or may be a mixture of two or more.
  • R 27 in the general formula (8) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 6 or more carbon atoms, usually 7 to 30, preferably 8 to 20 Long chain alkyl groups.
  • the alkyl group of R 27 is same as in the case of R 26, alone may be, or may be a mixture of two or more.
  • the molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units represented by the formulas (7) and (8).
  • the term “substantially” as used herein refers to the copolymer. It means that the sum of the monomer units of the formula (7) and the formula (8) present therein exceeds 50% by mass.
  • the sum of the monomer units of the formulas (7) and (8) is preferably 70% by mass or more.
  • the abundance ratio of the monomer unit of the formula (7) and the monomer unit of the formula (8) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40, in terms of mass ratio.
  • Examples of monomer units other than the formulas (7) and (8) that may be contained in the copolymer include ⁇ such as acrylic acid and methacrylic acid. , ⁇ -unsaturated carboxylic acids; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether, etc. And other monomer units derived from acrylonitrile, styrene, ⁇ -methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.
  • crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group (meta )
  • the acrylate polymer for example, it has a crosslinkable silicon group described in JP-A No.
  • the molecular chain has substantially (1) an alkyl group having 1 to 8 carbon atoms (meta (Meth) acrylic acid ester-based copolymers containing an acrylic acid alkyl ester monomer unit and (2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms These (meth) acrylic acid ester copolymers can also be used.
  • the number average molecular weight of the (meth) acrylic acid ester polymer is preferably 600 to 10,000, more preferably 600 to 5,000, and still more preferably 1,000 to 4,500. By setting the number average molecular weight within this range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group can be improved.
  • the (meth) acrylic acid ester polymer may be used alone or in combination of two or more.
  • the compounding ratio of the polyoxyalkylene polymer having the crosslinkable silicon group and the (meth) acrylic acid ester polymer having the crosslinkable silicon group is not particularly limited, but the (meth) acrylic acid ester
  • the (meth) acrylic acid ester polymer is preferably in the range of 10 to 60 parts by mass, more preferably 20 to 20 parts by mass with respect to 100 parts by mass in total of the polymer and the polyoxyalkylene polymer. It is within the range of 50 parts by mass, and more preferably within the range of 25 to 45 parts by mass. If the amount of the (meth) acrylic acid ester polymer is more than 60 parts by mass, the viscosity becomes high and workability deteriorates, which is not preferable.
  • a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, in the presence of an organic polymer having a crosslinkable silicon group (A method of polymerizing a meth) acrylate monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.
  • a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a crosslink with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group is preferably used in an amount of 10 to 200 parts by weight, more preferably 20 to 80 parts by weight.
  • epoxy resin curing agent known epoxy resin curing agents can be widely used and are not particularly limited.
  • epoxy resin curing agents can be widely used and are not particularly limited.
  • Aliphatic amines such as diamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, oleylamine, etc .; mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1 , 2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, polycyclohexylpolyamine, 1,8-diazabi Cycloaliphatic amines such as chloro [5,4,0] undecene-7 (DBU); aromatic amines such as metaphenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone; m -Aliphatic amines such as
  • curing agents for epoxy resins 2,4,6-tris (dimethylaminomethyl) phenol and polyoxypropylene-based diamine are preferable from the viewpoint of curability and physical property balance.
  • These curing agents may be used alone or in combination of two or more.
  • the amount of the epoxy resin curing agent is 1 to 60 parts by mass of the epoxy resin curing agent with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. 2 to 50 parts by mass is preferable, and 4 to 40 parts by mass is more preferable.
  • the curable composition of the present invention includes, in addition to the above-described components, other curing catalysts, fillers, diluents, water, ultraviolet absorbers, antioxidants, anti-aging agents, and adhesion imparting agents as necessary. , Physical property modifiers, plasticizers, thixotropic agents, dehydrating agents (storage stability improvers), flame retardants, tackifiers, anti-sagging agents, colorants, radical polymerization initiators, etc. Other compatible polymers may be blended.
  • known curing catalysts can be widely used as long as they do not affect the performance of the curable composition, and are not particularly limited.
  • organometallic compounds and amines can be mentioned.
  • silanol condensation catalyst it is preferable to use a silanol condensation catalyst.
  • silanol condensation catalyst examples include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; dibutyltin diacetyl Chelate compounds such as acetonate, dibutyltin diethyl acetoacetate, zirconium tetraacetylacetonate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmer Rate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate
  • the physical properties such as viscosity can be adjusted by blending the diluent.
  • diluent known diluents can be widely used, and are not particularly limited.
  • saturated hydrocarbon solvents such as normal paraffin and isoparaffin, linearlen dimer (trade name of Idemitsu Kosan Co., Ltd.), etc.
  • ⁇ -olefin derivatives aromatic hydrocarbon solvents such as toluene, xylene, alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, diacetone alcohol, ethyl acetate, butyl acetate, amyl acetate,
  • solvents such as ester solvents such as cellosolve acetate, citrate solvents such as acetyltriethyl citrate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable.
  • Normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms. Specifically, N-11 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number 11, flash point 68 ° C.), N-12 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number) 12, flash point 85 ° C.), IP solvent 2028 (isoparaffin, manufactured by Idemitsu Kosan Co., Ltd., carbon number 10 to 16, flash point 86 ° C.) and the like.
  • filler examples include reinforcing fillers such as fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolin, titanium oxide. Further, fillers such as calcium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, shirasu balloon, organic balloon, organic fiber and inorganic fiber can be used.
  • fillers such as calcium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, shirasu balloon, organic balloon, organic fiber and inorganic fiber can be used.
  • fillers mainly fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and
  • a filler selected from activated zinc white is used in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer, preferable results are obtained.
  • a filler selected mainly from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like is used. Preferred results can be obtained by using it in the range of 5 to 500 parts by mass per 100 parts by mass of the same polymer.
  • These fillers may be used alone or in combination of two or more.
  • the antioxidant is used to prevent oxidation of the curable composition to improve weather resistance and heat resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. It is done.
  • the ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the curable composition, for example, ultraviolet absorption of benzotriazole, triazine, benzophenone, benzoate, etc. Agents and the like.
  • the anti-aging agent is used for preventing heat deterioration of the curable composition and improving the heat resistance.
  • an anti-aging agent such as an amine-ketone type or an aromatic secondary amine type is used.
  • Antiaging agents, benzimidazole type antiaging agents, thiourea type antiaging agents, phosphorous acid type antiaging agents and the like can be mentioned.
  • the plasticizer is added for the purpose of improving elongation physical properties after curing or adjusting the hardness to reduce the modulus.
  • the type of the plasticizer is not particularly limited.
  • phthalates such as diisoundecyl phthalate; aliphatic dibasic esters such as dioctyl adipate; glycol esters such as diethylene glycol dibenzoate Aliphatic esters such as butyl oleate; Phosphate esters such as tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil; Polyester plasticizers; Polyethers such as polypropylene glycol derivatives Polyoxyethylene alkyl ethers such as tetraethylene glycol diethyl ether; polystyrene oligomers such as poly- ⁇ -methylstyrene; hydrocarbon oligomers such as polybutadiene; chlorinated paraffins; UP-1080 ( Acrylic plasticizers such as Toagosei Co.,
  • thixotropic agent examples include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate.
  • the dehydrating agent is added for the purpose of removing moisture during storage.
  • Examples of the dehydrating agent include zeolite, calcium oxide, magnesium oxide, and zinc oxide.
  • the flame retardant examples include metal hydroxides such as aluminum hydroxide and magnesium hydroxide; phosphorus flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide flame retardants such as antimony trioxide; Flame retardants; chlorine flame retardants and the like.
  • Adhesive agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- Amino group-containing silanes such as ( ⁇ -aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; Epoxy group-containing silanes such as glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ - (3,4-e
  • the adhesiveness-imparting agent is added too much, the modulus of the cured product is increased, and if it is too small, the adhesiveness is lowered. Therefore, 0.1 to 15 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. It is preferable to add part, more preferably 0.5 to 10 parts by weight.
  • a tackifier is preferable for improving the wettability of the adherend and increasing the peel strength.
  • examples include, but are not limited to, petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin and its phenolic resin copolymer, phenol / phenol novolac resin-based tackifier resin, etc. It is not something.
  • the curable composition of the present invention can be cured at normal temperature by moisture in the atmosphere, and is suitably used as a normal temperature moisture-curable curable composition, but if necessary, curing is accelerated by heating as appropriate. You may let them.
  • the curable composition of the present invention can be used as an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, and the like. Since the curable composition of the present invention is excellent in adhesiveness, storage stability, and curability, it is particularly preferable to use it as an adhesive, but for various other buildings, automobiles, civil engineering, electric / electronics. It can be used for fields.
  • each compounding substance is shown by a mass part. Details of each compounding substance are as follows. * 1) Dioctyltin oxide: Product name “Neostan U-800P” manufactured by Nitto Kasei Co., Ltd. * 2) Diphenyldimethoxysilane: Trade name “Shin-Etsu Silicone KBM-202SS”, manufactured by Shin-Etsu Chemical Co., Ltd. * 3) Phenylmethyldimethoxysilane: Trade name “Shin-Etsu Silicone KBM-102”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Phenyltrimethoxysilane Trade name “Shin-Etsu Silicone KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd. * 5) Vinyltrimethoxysilane: Trade name “Shin-Etsu Silicone KBM-1003”, manufactured by Shin-Etsu Chemical Co., Ltd. * 6) Decyltrimethoxysilane: Trade name “Shin-Etsu Silicone KBM-3103C”, manufactured by Shin-Etsu Chemical Co., Ltd. * 10) 3-Glycidoxypropyltrimethoxysilane, trade name “Shin-Etsu Silicone KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd. * 17) Vinyltriethoxysilane: Trade name “Shin-Etsu Silicone KBE-1003”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Synthesis Example 2 Add a methanol solution of sodium methoxide (NaOMe) to polyoxypropylene diol having a molecular weight smaller than that of the polyoxypropylene diol used in Synthesis Example 1 to distill off the methanol, and then add allyl chloride to remove the terminal hydroxyl group. Converted to the base. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal.
  • NaOMe sodium methoxide
  • Example 1 Each compounding substance was mixed by the compounding ratio shown in Table 2, and it deaerated and stirred at 25 degreeC, and prepared A agent and B agent. The following measurements were performed on the obtained agent A and agent B. The results are shown in Table 3.
  • TFT Tack free time
  • Adhesion conditions and measurement conditions are as follows. Adherent: 5 mm thick mild steel plate 25 mm ⁇ 100 mm. -Adhesive conditions A agent and B agent were measured so that it might become 1: 1 weight ratio, and it mixed on the conditions of 500 rpm of revolutions, and 1000 rpm of revolutions for 2 minutes using the vacuum planetary stirrer. The mixture was applied to the surface of the adherend, spread thinly, bonded together under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and pressed in two places with a 30 mm wide eyeball clip so that the thickness of the adhesive layer was 0.1 mm. .
  • the bonding area was 12.5 mm ⁇ 25 mm.
  • the bonded adherends were allowed to stand for 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50% to obtain test bodies for a tensile shear test. -Measurement conditions About the obtained test body, the test shear rate was 50 mm / min and the tensile shear bond strength in 23 degreeC was measured.
  • Tin-based curing catalysts B1 to B4 are tin-based curing catalysts B1 to B4 obtained in Production Examples 1 to 4, respectively.
  • Polymer P1 is polymer P1 obtained in Synthesis Example 1, and details of the compounding substances are as follows. It is as follows. * 7) Bisphenol A type epoxy resin: trade name “jER828”, manufactured by Mitsubishi Chemical Corporation, number average molecular weight of about 370. * 8) Hydrogenated bisphenol A type epoxy resin: Trade name “ADEKA RESIN EP-4080E”, manufactured by ADEKA Corporation, number average molecular weight of about 350.
  • Polyethylene glycol skeleton epoxy resin Trade name “Adeka Resin ED-506” , Manufactured by ADEKA Corporation, ethylene glycol diglycidyl ether, number average molecular weight of about 620. * 10) KBM-403: 3-glycidoxypropyltrimethoxysilane, trade name “Shin-Etsu Silicone KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd. * 11)
  • SAT200 A polymer whose main chain is polyoxypropylene and has a dimethoxysilyl group at the molecular end, trade name “Syryl SAT200”, manufactured by Kaneka Corporation.
  • EH30 2,4,6-trisdimethylaminomethylphenol, trade name “Versamine EH-30”, manufactured by Cognis Japan.
  • KBM-603 N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, trade name “Shin-Etsu Silicone KBM-603”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 4. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 5.
  • Tin-based curing catalysts B5 to 8 are tin-based curing catalysts B5 to 8 obtained in Production Examples 5 to 8, respectively, and the details of each compounding substance are the same as in Table 2.
  • Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 6. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 7.
  • Tin-based curing catalysts B9 and B are tin-based curing catalysts B9 and 10 obtained in Production Examples 9 and 10, respectively, and the details of each compounding substance are the same as in Table 2.
  • Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 8. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 9.
  • Tin-based curing catalysts B1 and B11 to B13 are tin-based curing catalysts B1 and B11 to B13 obtained in Production Examples 1 and 11 to 13, respectively.
  • Polymers P1 to P3 are obtained in Synthesis Examples 1 to 3, respectively.
  • Polymers P1 to P3, and details of each compounding substance are the same as in Table 2. Details of other compounding substances are as follows.
  • MA440 a mixture of a polymer having a main chain of polyoxypropylene and having a methyldimethoxysilyl group at the molecular end and a polymer having a main chain of a polymethacrylic acid ester and having a methyldimethoxysilyl group in the molecule; Product name “Cyrill MA440”, manufactured by Kaneka Corporation.
  • XMAP SA120S (meth) acrylic acid ester copolymer having a methyldimethoxysilyl group, trade name “XMAP SA120S”, manufactured by Kaneka Corporation.
  • EP505S A polymer containing 33% by mass of process oil, the main chain of which is polyisobutylene and having a methyldimethoxysilyl group at the molecular end, trade name “Epion EP505S”, manufactured by Kaneka Corporation.
  • each compounding substance is shown by g. Details of each compounding substance are the same as those in Table 2, and details of other compounding substances are as follows. * 15) U810: Dioctyltin dilaurate, trade name “Neostan U-810”, manufactured by Nitto Kasei Co., Ltd. * 16) S-1: Reaction product of dioctyltin salt and normal ethyl silicate, trade name “Neostan S-1”, manufactured by Nitto Kasei Co., Ltd.
  • Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 12. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 13.
  • each compounding substance is indicated by g. Details of each compounding substance are the same as those in Tables 2, 8 and 10.

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Abstract

L'invention fournit une composition durcissable à deux composants permettant de promouvoir un haut niveau de sécurité ainsi qu'une vitesse de durcissement, et présentant une excellente stabilité de stockage, l'invention fournit également un produit durci constitué par durcissement de cette composition. La composition durcissable à deux composants est constituée : d'un agent (A) contenant une résine époxy et un catalyseur de durcissement à base d'étain liquide ; et d'un agent (B) contenant un polymère organique comprenant un groupe silicium réticulable et un durcisseur pour résine époxy. Ledit catalyseur de durcissement à base d'étain liquide consiste en un produit réactionnel constitué par réaction d'un composé alcoxysilane spécifique, et d'au moins une sorte de composé étain choisie dans un groupe constitué d'un oxyde d'étain dioctylique et d'un carboxylate d'étain dioctylique. Pour 100 parties en masse dudit polymère organique comprenant un groupe silicium réticulable, la teneur en résine époxy est de 10 à 200 parties en masse, la teneur en catalyseur de durcissement à base d'étain liquide est de 0,1 à 20 parties en masse, et la teneur en durcisseur pour résine époxy est de 1 à 60 parties en masse.
PCT/JP2013/066650 2012-07-25 2013-06-18 Composition durcissable à deux composants WO2014017218A1 (fr)

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JP2017536440A (ja) * 2014-10-01 2017-12-07 シーカ テクノロジー アクチェンゲゼルシャフト ２剤の組合せ
WO2022215521A1 (fr) * 2021-04-08 2022-10-13 株式会社スリーボンド Composition de résine durcissable en deux parties et produit durci correspondant
WO2022215522A1 (fr) * 2021-04-08 2022-10-13 株式会社スリーボンド Composition de résine durcissable bicomposant et produit durci associé

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JP2011127007A (ja) * 2009-12-18 2011-06-30 Cemedine Co Ltd 耐熱性が改善された硬化性組成物
JP2012001614A (ja) * 2010-06-16 2012-01-05 Cemedine Co Ltd 貯蔵安定性に優れる難燃伝熱性硬化性組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017536440A (ja) * 2014-10-01 2017-12-07 シーカ テクノロジー アクチェンゲゼルシャフト ２剤の組合せ
WO2022215521A1 (fr) * 2021-04-08 2022-10-13 株式会社スリーボンド Composition de résine durcissable en deux parties et produit durci correspondant
WO2022215522A1 (fr) * 2021-04-08 2022-10-13 株式会社スリーボンド Composition de résine durcissable bicomposant et produit durci associé

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