WO2014200100A1 - 接着剤組成物 - Google Patents
接着剤組成物 Download PDFInfo
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- WO2014200100A1 WO2014200100A1 PCT/JP2014/065801 JP2014065801W WO2014200100A1 WO 2014200100 A1 WO2014200100 A1 WO 2014200100A1 JP 2014065801 W JP2014065801 W JP 2014065801W WO 2014200100 A1 WO2014200100 A1 WO 2014200100A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
- C09J2463/003—Presence of epoxy resin in the primer coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2471/00—Presence of polyether
- C09J2471/003—Presence of polyether in the primer coating
Definitions
- the present invention relates to an adhesive composition that can form an adhesive layer that has excellent adhesive strength under cold conditions and can maintain excellent adhesive strength even when contacted with alkaline moisture.
- an outer wall finishing material for example, a tile or the like is bonded and integrated to the concrete surface via an adhesive layer.
- the adhesive layer can be obtained by applying an adhesive composition to a concrete surface and then curing it.
- an adhesive composition (a) an oxyalkylene polymer containing a reactive silicon group, (b) a reaction product of dibutyltin salt and normal ethyl silicate, (c) an epoxy resin, (d) ( A moisture curable resin composition containing a ketimine compound that serves as a latent curing agent in c) is used (for example, Patent Document 1).
- an object of the present invention is to provide an adhesive composition having excellent adhesive strength under cold conditions and excellent adhesive strength despite contact with alkaline moisture.
- the adhesive composition of the present invention comprises 100 parts by weight of a polyalkylene oxide having a hydrolyzable silyl group, 1 to 20 parts by weight of an epoxy resin, 0.1 to 10 parts by weight of an epoxy silane coupling agent, 0.5 to 0.5 parts of a ketimine compound. It contains 20 parts by weight and 1 to 100 parts by weight of fatty acid-treated calcium oxide.
- the adhesive composition of the present invention can form an adhesive layer having excellent adhesive strength after curing.
- the adhesive composition of the present invention can form an adhesive layer having excellent adhesive strength under both cold conditions and room temperature conditions.
- the adhesive composition of the present invention even when it is placed in a harsh environment exposed to rainwater such as outdoors or in a cold region for a long period of time, the adhesive layer and the concrete or Peeling from the outer wall finishing material is reduced, and the excellent aesthetics of the outer wall finishing material can be maintained over a long period of time.
- the adhesive composition of the present invention contains a polyalkylene oxide having a hydrolyzable silyl group.
- the polyalkylene oxide has a hydrolyzable silyl group at the terminal or side chain of the polyalkylene oxide chain. Having a hydrolyzable silyl group in the side chain of the polyalkylene oxide chain means that the polyalkylene oxide chain has a hydrolyzable silyl group as a side chain and the side chain of the polyalkylene oxide chain. It includes both cases where some have hydrolyzable silyl groups.
- the hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom.
- the hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and examples thereof include a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. . Of these, an alkoxy group is preferable. Alkoxy groups are less likely to produce harmful byproducts after the reaction.
- alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; dimethoxysilyl groups such as dimethoxymethylsilyl group and diethoxymethylsilyl group And monoalkoxysilyl groups such as a methoxydimethoxysilyl group and an ethoxydimethylsilyl group. Of these, a dimethoxysilyl group and a trimethoxysilyl group are particularly preferable.
- the average number of hydrolyzable silyl groups per molecule of polyalkylene oxide is preferably 1 to 2. More preferably, the polypropylene oxide has hydrolyzable silyl groups at both ends of the main chain. According to such an adhesive composition containing polypropylene oxide, an adhesive layer that maintains excellent adhesive strength even in the presence of alkaline moisture and maintains excellent adhesive strength even in cold conditions is formed. can do.
- the average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide is the concentration of hydrolyzable silyl groups in the polyalkylene oxide determined by 1 H-NMR and the polyalkylene determined by the GPC method. It can be calculated based on the number average molecular weight of the oxide.
- the main chain skeleton of the polyalkylene oxide having a hydrolyzable silyl group has a general formula: — (R—O) n — (wherein R represents an alkylene group having 1 to 14 carbon atoms, and n represents a repeating unit) And a polymer containing a repeating unit represented by the following formula:
- the main chain skeleton of the polyalkylene oxide may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
- polyalkylene oxide examples include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. Of these, polypropylene oxide is preferable. According to the adhesive composition containing polypropylene oxide, it is possible to form an adhesive layer that maintains excellent adhesive strength despite the presence of alkaline moisture and maintains excellent adhesive strength even under cold conditions. it can.
- the number average molecular weight of the polyalkylene oxide is preferably 3,000 to 50,000, and more preferably 10,000 to 20,000. If the number average molecular weight is too large, the polyalkylene oxide may increase the viscosity of the adhesive composition and reduce the coating property of the adhesive composition. In addition, when the number average molecular weight of the polyalkylene oxide is too small, the adhesive composition containing such a polyalkylene oxide is likely to form an adhesive layer that is hard and brittle and has low adhesive strength under cold conditions. is there.
- the number average molecular weight of a polyalkylene oxide is the value measured by polystyrene conversion by GPC (gel permeation chromatography) method. Specifically, 6 to 7 mg of polyalkylene oxide is collected, and the collected polyalkylene oxide is supplied to a test tube. Prepare an orthodichlorobenzene (o-DCB) solution containing 0.05% by weight of dibutylhydroxytoluene (BHT) and add this solution to a test tube to dilute the polyalkylene oxide concentration to 1 mg / mL. To prepare a diluted solution. The dilution liquid is shaken for 1 hour at a rotation speed of 25 rpm at 145 ° C. using a dissolution filter, and the polyalkylene oxide is dissolved in the solution to obtain a measurement sample. Using this measurement sample, the number average molecular weight of the polyalkylene oxide can be measured by the GPC method.
- o-DCB orthodichlorobenzene
- BHT dibut
- the number average molecular weight of the polyalkylene oxide can be measured, for example, with the following measuring apparatus and measurement conditions.
- Product name “HLC-8121GPC / HT” manufactured by TOSOH Measurement conditions Column: TSKgelGMHHR-H (20) HT x 3 TSK guard column-HHR (30) HT x 1
- Detector Bryce refractometer Standard material: Polystyrene (Molecular weight: 500 to 8420000, manufactured by TOSOH) Elution conditions: 145 ° C
- polyalkylene oxide having a hydrolyzable silyl group a commercially available product can be used.
- trade names MS polymer S-203, S-303 manufactured by Kaneka Corp . silyl polymer SAT-200, SAT-350, SAT-400; trade names manufactured by Asahi Glass Co., Ltd. Exstar ESS-3620, ESS-2420, ESS 2410, ESS 3430 Etc.
- polyalkylene oxide having a trialkoxysilyl group via a urethane bond at both ends of the polyalkylene oxide chain can be used.
- a polyalkylene oxide having a trimethoxysilyl group via a urethane bond at both ends of the polyalkylene oxide chain is preferred.
- adhesion that maintains excellent adhesive strength despite the presence of alkaline water and maintains excellent adhesive strength even under cold conditions An agent layer can be formed.
- the trialkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group.
- the polyalkylene oxide having a trialkoxysilyl group via a urethane bond at both ends of the polyalkylene oxide chain is, for example, a trimethoxysilyl group and an isocyanate group on both hydroxy groups of a polyalkylene oxide having a hydroxy group at both ends. It is obtained by reacting a compound having
- Polyalkylene oxides having hydroxy groups at both ends include polyethylene oxide glycol (polyoxyethylene glycol), polypropylene oxide glycol (polyoxypropylene glycol), polypropylene oxide glycol (polyoxybutylene glycol), polytetramethylene oxide glycol (poly Oxytetramethylene glycol), polyethylene oxide-polypropylene oxide glycol (polyoxyethylene-polyoxypropylene glycol), and polypropylene oxide-polybutylene oxide glycol (polyoxypropylene-polyoxybutylene glycol).
- Examples of the compound having a trialkoxysilyl group and an isocyanate group include 1-isocyanate methyltrimethoxysilane, 2-isocyanateethyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatobutyltrimethoxysilane, 3-isocyanatepentyltril.
- Methoxysilane 1-isocyanatopropyltrimethoxysilane, 1-isocyanatemethyltriethoxysilane, 2-isocyanateethyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatebutyltriethoxysilane, 3-isocyanatepentyltriethoxysilane 1-isocyanatopropyltriethoxysilane and the like.
- a polyalkylene oxide having a trialkoxysilyl group at both ends of the polyalkylene oxide chain via a urethane bond a polyalkylene oxide having a hydroxy group at both ends, a compound having a trialkoxysilyl group and an isocyanate group Is mixed to obtain a mixture, and this mixture is stirred to react a hydroxyl group at both ends of the polyalkylene oxide with an isocyanate group of the above compound to form a urethane bond. Moreover, reaction can be accelerated
- polyalkylene oxide having a trialkoxysilyl group via a urethane bond at both ends of the polyalkylene oxide chain a commercially available product can be used.
- a polyalkylene oxide having a main chain skeleton of polypropylene oxide and having trimethoxysilyl groups via urethane bonds at both ends of the main chain skeleton Desmosal (registered trademark) XP2749 manufactured by Bayer Co., Ltd. may be mentioned. .
- the adhesive composition may contain a (meth) acrylate polymer as necessary.
- the (meth) acrylate polymer has a trialkoxysilyl group in the side chain or terminal of the main chain skeleton.
- the main chain skeleton of the (meth) acrylate polymer is a monomer copolymer containing methyl (meth) acrylate and butyl (meth) acrylate, and a monomer copolymer containing methyl methacrylate and butyl acrylate A copolymer of monomers including methyl methacrylate and n-butyl acrylate is more preferable.
- the adhesive layer has excellent weather resistance and maintains excellent adhesive strength despite the presence of alkaline moisture.
- An adhesive layer can be formed.
- (meth) acrylate means a methacrylate and / or an acrylate.
- the trialkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group.
- the content of the methyl (meth) acrylate component is preferably 3 to 70% by weight, more preferably 5 to 50% by weight.
- the content of the methyl (meth) acrylate component is 3% by weight or more, an adhesive layer excellent in weather resistance can be formed.
- the content of the methyl (meth) acrylate component is 70% by weight or less, the adhesive composition has excellent workability.
- the content of the butyl (meth) acrylate component is preferably 30 to 97% by weight, and more preferably 50 to 95% by weight.
- the adhesive composition has excellent workability.
- the content of the butyl (meth) acrylate component is 97% by weight or less, an adhesive layer having excellent weather resistance can be formed.
- the monomer used in the copolymer constituting the main chain skeleton includes other monomers in addition to methyl (meth) acrylate, butyl acrylate, and butyl methacrylate. You may go out.
- examples of other monomers include styrene such as styrene, indene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and divinylbenzene.
- the polymerization method of the (meth) acrylate polymer is not particularly limited, and a known method can be used.
- a free radical polymerization method an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, a living anion polymerization method can be used.
- examples include various polymerization methods such as a combination method, a living cationic polymerization method, and a living radical polymerization method.
- the (meth) acrylate polymer has a trialkoxysilyl group at the end or side chain of the main chain skeleton.
- the (meth) acrylate polymer preferably has a trimethoxysilyl group in the side chain or terminal of the main chain skeleton.
- the side chain of the main chain skeleton has a trialkoxysilyl group means that the main chain skeleton has a trialkoxysilyl group as a side chain, The case where both have a trialkoxysilyl group in a part of the side chain is included.
- the method for introducing a trialkoxysilyl group into a (meth) acrylate polymer is not particularly limited.
- the copolymer of monomers including methyl (meth) acrylate, butyl acrylate, and butyl methacrylate is unsaturated.
- Examples thereof include a method of hydrosilylating by introducing a hydrosilane having a trialkoxysilyl group after introducing a group.
- the weight average molecular weight of the (meth) acrylate polymer is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and particularly preferably 3,000 to 15,000. According to the (meth) acrylate polymer having a weight average molecular weight within the above range, the adhesive composition is excellent in workability.
- the content of the (meth) acrylate polymer in the adhesive composition is preferably 5 to 300 parts by weight and more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group. Preferably, 30 to 100 parts by weight is particularly preferable.
- the content of the (meth) acrylate polymer in the adhesive composition is 5 parts by weight or more, an adhesive layer that maintains excellent adhesive strength despite the presence of alkaline water and has excellent weather resistance Form.
- the content of the (meth) acrylate polymer in the adhesive composition is 300 parts by weight or less, the adhesive composition is excellent in workability.
- Epoxy resin The adhesive composition of the present invention contains an epoxy resin.
- Epoxy resins include bisphenol A type epoxy resin, which is a reaction product of bisphenol A and epichlorohydrin, bisphenol F type epoxy resin, which is a reaction product of bisphenol F and epichlorohydrin, and an epoxy resin hydrogenated to these.
- bisphenol A type epoxy resins are preferred. According to the bisphenol A type epoxy resin, the adhesive layer obtained by curing the adhesive composition maintains excellent adhesive strength despite the presence of alkaline moisture, and excellent adhesive strength even under cold conditions. Is preferable.
- the epoxy equivalent of the epoxy resin is preferably 180 to 200 g / eq, and more preferably 185 to 195 g / eq. According to the adhesive composition containing an epoxy resin having an epoxy equivalent in the above range, an adhesive layer excellent in mechanical strength and toughness can be formed.
- the “epoxy equivalent” is a value obtained by dividing the molecular weight of the epoxy compound by the number of epoxy groups in one molecule.
- the epoxy equivalent of the epoxy resin is a value measured according to JIS K7236 (2009).
- the content of the epoxy resin in the adhesive composition is 1 to 20 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group, and 10 to 20 parts by weight. Part is more preferred.
- the adhesive layer that maintains excellent adhesive strength even in the presence of alkaline moisture and maintains excellent adhesive strength even under cold conditions. Can be formed.
- the adhesive composition of the present invention contains a ketimine compound.
- a ketimine compound means a dehydration condensate of an amine compound having two or more amino groups in one molecule and a ketone compound. Ketimine compounds are used as latent curing agents. In the absence of moisture, the ketimine compound itself is stably present in the adhesive composition without reacting with the epoxy resin. However, the ketimine compound reacts with moisture such as moisture in the air to form a primary amine. This primary amine can react with the epoxy resin to accelerate the curing of the adhesive composition.
- Preferred ketimine compounds include the following compounds. 2,5,8-triaza-1,8-nonadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,10-diphenyl-3,6,9-triaza-2,9-undecadiene, 3,11-dimethyl-4,7,10-triaza-3,10-tridecadiene, 3,11-diethyl-4,7,10-triaza-3,10-tridecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadien, 2,4,20,22-tetramethyl-5,12,19-triaza-4,19-trieicosadiene and 2,4,15,17-tetramethyl-5,8,11,14-tetraaza- 4,14-Octadecadien.
- the ketimine compounds may be used alone or in combination of two or more. Of these, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene is preferred as the ketimine compound.
- the molar ratio [(total number of moles of epoxy groups of epoxy resin) / (total number of moles of amino groups contained in the amine compound which is a hydrolyzate of ketimine compound)] Since the adhesive layer obtained by curing the composition maintains excellent adhesive strength despite the presence of alkaline water and maintains excellent adhesive strength even under cold conditions, 0.7 or more is preferable. 0.0 or more is more preferable.
- the molar ratio [(total number of moles of epoxy groups of the epoxy resin) / (total number of moles of amino groups of the amine compound which is a hydrolyzate of the ketimine compound)]
- the adhesive layer obtained by curing the agent composition maintains excellent adhesive strength despite the presence of alkaline water and maintains excellent adhesive strength even under cold conditions, so 1.2 or less is preferable.
- the molar ratio [(total number of moles of epoxy groups of epoxy resin) / (total number of moles of amino groups of amine compound which is a hydrolyzate of ketimine compound)] is 0.7 or less. This means that the number of groups is 1 and the number of epoxy groups is 0.7 or less.
- the molar ratio [(total number of moles of epoxy groups of epoxy resin) / (total number of moles of amino groups contained in the amine compound which is a hydrolyzate of ketimine compound)] is the above preferred range.
- the adhesive strength is further improved despite the presence of alkaline moisture, and even better in cold conditions.
- An adhesive layer can be formed to maintain.
- the total number of moles of epoxy groups of the epoxy resin and the total number of moles of amino groups possessed by the amine compound can be calculated from the molecular weight and the number of functional groups of the epoxy resin or amine compound. That is, the total number of moles of epoxy groups in the epoxy resin is a value obtained by dividing the content of the epoxy resin by the epoxy equivalent.
- the total number of moles of amino groups possessed by the amine compound is a value obtained by dividing the amount of the amine compound produced by hydrolysis of the ketimine compound by the amine equivalent.
- the amine equivalent of the amine compound is a value measured according to JIS K7237 “Testing method for total amine value of amine-based curing agent for epoxy resin”.
- the content of the ketimine compound in the adhesive composition is 0.5 to 20 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group. According to the adhesive composition in which the ketimine compound content is within the above range, the adhesive layer obtained by curing the adhesive composition maintains excellent adhesive strength despite the presence of alkaline moisture, and Maintains excellent adhesive strength even under cold conditions.
- the adhesive composition of the present invention contains fatty acid-treated calcium oxide. According to the adhesive composition containing fatty acid-treated calcium oxide, the adhesive layer obtained by curing the adhesive composition maintains excellent adhesive strength despite the presence of alkaline moisture, and even under cold conditions. Maintains excellent adhesive strength.
- Fatty acid-treated calcium oxide is calcium oxide whose surface is treated with fatty acid.
- the fatty acid include saturated fatty acids such as decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and icosanoic acid; hexadecenoic acid, octadecenoic acid, octadecadienoic acid, octadecatrienoic acid And unsaturated fatty acids such as icosanoic acid, icosadienoic acid, icosatrienoic acid, icosatetratrienoic acid, and tetradocosanoic acid. These fatty acids may be used alone or in combination of two or more. Of these, octadecanoic acid is preferred. Octadecanoic acid is excellent in compatibility with the above
- the average particle size of the fatty acid-treated calcium oxide is preferably 0.05 to 100 ⁇ m, more preferably 1 to 50 ⁇ m.
- Fatty acid-treated calcium oxide having an average particle size within the above range can be highly dispersed in the adhesive composition, thereby maintaining excellent adhesive strength despite the presence of alkaline moisture and cooling conditions It is possible to form an adhesive layer that maintains excellent adhesive strength even underneath.
- the average particle diameter of the fatty acid-treated calcium oxide can be measured using a laser diffraction / scattering particle size analyzer. For example, after adding fatty acid-treated calcium oxide to methanol so that its concentration becomes 10% by weight, an ultrasonic homogenizer is used to irradiate ultrasonic waves at an output of 1 kW for 10 minutes to obtain a suspension.
- the volume particle size distribution of the fatty acid-treated calcium oxide is measured with a laser diffraction / scattering particle size analyzer (for example, device life “SACD-2100” manufactured by Shimadzu Corporation) for the liquid, and the cumulative 50% value of the volume particle size distribution is measured. It can be calculated as the average particle size of the fatty acid-treated calcium oxide.
- the content of the fatty acid-treated calcium oxide in the adhesive composition is such that the adhesive layer obtained by curing the adhesive composition with respect to 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group has the presence of alkaline moisture. Nevertheless, it maintains 1 to 100 parts by weight, preferably 20 to 100 parts by weight, and more preferably 40 to 100 parts by weight because it maintains excellent adhesive strength and maintains excellent adhesive strength even under cold conditions. .
- the adhesive composition of the present invention contains an epoxy silane coupling agent.
- the epoxy silane coupling agent means a compound containing a silicon atom having an alkoxy group bonded in one molecule and a functional group having an epoxy group. According to the epoxy silane coupling agent, it is possible to form an adhesive layer that maintains excellent adhesive strength despite the presence of alkaline moisture and maintains excellent adhesive strength even under cold conditions.
- epoxy silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylethyldisilane. Examples thereof include ethoxysilane, and 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane.
- An epoxy silane coupling agent may be used individually by 1 type, or 2 or more types may be used together. Of these, 3-glycidoxypropyltrimethoxysilane is preferable.
- the content of the epoxy silane coupling agent in the adhesive composition forms an adhesive layer that maintains excellent adhesive strength despite the presence of alkaline moisture and maintains excellent adhesive strength even in cold conditions. Therefore, it is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight based on 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group.
- the adhesive composition of the present invention preferably contains a silanol condensation catalyst.
- the silanol condensation catalyst is a catalyst for promoting a dehydration condensation reaction between silanol groups formed by hydrolyzing a hydrolyzable silyl group of polyalkylene oxide.
- the silanol group means a hydroxy group ( ⁇ Si—OH) directly bonded to a silicon atom.
- silanol condensation catalyst examples include 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate bis (dibutyltin laurin).
- a silanol condensation catalyst may be used independently and 2 or more types may be used together.
- the content of the silanol condensation catalyst in the adhesive composition is preferably 0.1 to 3 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group. 1 to 2.5 parts by weight are particularly preferred.
- the time required for curing may be increased.
- the adhesive strength of the adhesive layer obtained by curing the adhesive composition is reduced by alkaline moisture, or the adhesive composition is cured. There is a possibility that the adhesive strength of the resulting adhesive layer under cold conditions may be reduced.
- the adhesive composition of the present invention may further contain other additives as required.
- additives include dehydrating agents, antioxidants, fillers, plasticizers, sagging inhibitors, ultraviolet absorbers, pigments, solvents, and fragrances.
- the adhesive composition of the present invention preferably further contains a dehydrating agent. According to the dehydrating agent, when the adhesive composition is stored, the adhesive composition can be prevented from being cured by moisture such as moisture in the air.
- dehydrating agents include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and methyl orthoformate And ester compounds such as ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate.
- dehydrating agents may be used alone or in combination of two or more. Of these, vinyltrimethoxysilane is preferable.
- the content of the dehydrating agent in the adhesive composition is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group. ⁇ 5 parts by weight is particularly preferred.
- the adhesive composition of the present invention preferably further contains an aminosilane coupling agent.
- the aminosilane coupling agent means a compound containing a silicon atom having an alkoxy group bonded in one molecule and a functional group having an amino group. According to the aminosilane coupling agent, when used in combination with the epoxysilane coupling agent, the adhesive layer obtained by curing the adhesive composition maintains excellent adhesive strength despite the presence of alkaline moisture and is cooled. Maintains excellent adhesive strength even under conditions.
- aminosilane coupling agents include N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ - Examples include aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and ⁇ -aminopropyltriethoxysilane.
- An aminosilane coupling agent may be used individually by 1 type, or 2 or more types may be used together. Of these, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane is preferable.
- the content of the aminosilane coupling agent in the adhesive composition is such that the adhesive layer obtained by curing the adhesive composition maintains excellent adhesive strength despite the presence of alkaline moisture, and even under cold conditions.
- the ratio of the total number of moles of epoxy groups in the epoxy silane coupling agent to the total number of moles of amino groups in the amino silane coupling agent ((of the epoxy groups in the epoxy silane coupling agent The total number of moles) / (total number of moles of amino groups in the aminosilane coupling agent)) is preferably 2.5 or more.
- epoxy silane coupling Ratio of the total number of moles of epoxy groups in the agent to the total number of moles of amino groups in the aminosilane coupling agent ((total number of moles of epoxy groups in the epoxysilane coupling agent) / (amino in the aminosilane coupling agent) The total number of moles of groups)) is preferably 5.0 or less, more preferably 3.0 or less.
- the ratio of the total number of moles of epoxy groups in the epoxy silane coupling agent to the total number of moles of amino groups in the amino silane coupling agent is 2.5 or more means that the number of amino groups is 1 and the number of epoxy groups is 2.5 or more.
- the total number of moles of epoxy groups in the epoxy silane coupling agent and the total number of moles of amino groups in the amino silane coupling agent can be calculated from the molecular weight and the number of functional groups of the epoxy silane coupling agent or amino silane coupling agent. That is, the total number of moles of epoxy groups in the epoxy silane coupling agent is a value obtained by dividing the content of the epoxy silane coupling agent by the epoxy equivalent.
- the total number of moles of amino groups in the aminosilane coupling agent is a value obtained by dividing the content of the aminosilane coupling agent by the amine equivalent.
- the epoxy equivalent of the epoxysilane coupling agent is a value measured according to JIS K7236 (2009).
- the amine equivalent of the aminosilane coupling agent is a value measured according to JIS K7237 “Testing method for total amine value of amine-based curing agent for epoxy resin”.
- the adhesive composition of the present invention preferably further contains an antioxidant.
- the antioxidant include hindered phenolic antioxidants, monophenolic antioxidants, bisphenolic antioxidants, and polyphenolic antioxidants. Of these, hindered phenol antioxidants are preferred. Specific examples of hindered phenol antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-).
- An antioxidant may be used individually by 1 type, or 2 or more types may be used together.
- the content of the antioxidant in the adhesive composition is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight with respect to 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group. preferable.
- the adhesive composition of the present invention preferably further contains a filler.
- the filler include calcium carbonate, magnesium carbonate, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, glass balloon and the like.
- a filler may be used individually by 1 type and 2 or more types may be used together.
- the adhesive composition of the present invention further contains a plasticizer. According to the adhesive composition containing the plasticizer, the adhesive layer obtained by curing the adhesive composition can maintain excellent adhesive strength over a long period even under cold conditions.
- plasticizer examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinormal hexyl phthalate, bis (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, and phthalic acid Phthalic acid esters such as dinonyl, diisodecyl phthalate, diisoundecyl phthalate, and bisbutylbenzyl phthalate; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol Can be mentioned. Of these, polyalkylene glycol is preferable, and polypropylene glycol is more preferable.
- the number average molecular weight of the polyalkylene glycol is preferably 1,000 to 10,000, and more preferably 2,000 to 5,000.
- the adhesive composition containing such a polyalkylene glycol has excellent adhesion even under cold conditions when the adhesive layer obtained by curing the polyalkylene glycol is cured. Maintain strength over a long period of time.
- the number average molecular weight of the polyalkylene glycol is a value obtained by converting the number average molecular weight of the polyalkylene oxide into polystyrene by GPC (gel permeation chromatography) method.
- GPC gel permeation chromatography
- the content of the plasticizer in the adhesive composition is preferably 1 to 50 parts by weight and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polyalkylene oxide having a hydrolyzable silyl group.
- the adhesive composition of the present invention may contain an anti-sagging agent.
- the sagging inhibitor include hydrogenated castor oil, fatty acid bisamide, and fumed silica.
- the adhesive composition of the present invention may contain an ultraviolet absorber.
- the ultraviolet absorber include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and benzotriazole ultraviolet absorbers.
- the adhesive composition of the present invention is suitably used for bonding and integrating an outer wall finish on a concrete surface. Specifically, after the adhesive composition is applied to the concrete surface, the outer wall finishing material is laminated on the applied adhesive composition, and these are left to cure to cure the adhesive composition. To form an adhesive layer. As a result, a building structure in which the outer wall finishing material is bonded and integrated on the concrete surface via the adhesive layer obtained by curing the adhesive composition is obtained.
- the outer wall finishing material for example, mortar, tile, brick, porcelain and stone are used.
- Examples 1 to 15 and Comparative Examples 1 to 7 The following components were blended in the blending amounts shown in Tables 1 to 3, and kneaded in a vacuum atmosphere for 60 minutes using a planetary mixer to obtain an adhesive composition.
- Polyalkylene oxide 1 polyalkylene oxide having a main chain skeleton made of polypropylene oxide and having a dimethoxysilyl group at the end of the main chain, an average number of dimethoxysilyl groups per molecule of 1.4, and a number average molecular weight of 20,000 , Product name "MS Polymer S-203" manufactured by Kaneka Chemical Co., Ltd.
- Polyalkylene oxide 2 polyalkylene oxide whose main chain skeleton is made of polypropylene oxide and has trimethoxysilyl groups at both ends of the main chain skeleton via urethane bonds, average of dimethoxysilyl groups per molecule Number 1.8, number average molecular weight 13,000, viscosity at 25 ° C.
- Tables 1 to 3 the total number of moles of epoxy groups of the epoxy resin (E1), the total number of moles of amino groups (A1) of the amine compound that is a hydrolyzate of the ketimine compound, and the moles thereof The ratio (E1 / A1) is shown respectively. Further, Tables 1 to 3 show the total number of moles of epoxy groups of the epoxysilane coupling agent (E2), the total number of moles of amino groups of the aminosilane coupling agent (A2), and the molar ratio (E2 / A2). Each is shown.
- the adhesive composition of the present invention forms an adhesive layer that is excellent in adhesive strength under both cold conditions and room temperature conditions, and maintains excellent adhesive strength even in contact with alkaline moisture. Can do. Therefore, the adhesive composition of the present invention can be used, for example, as an application for bonding and integrating an outer wall finishing material such as a tile on the surface of concrete constituting the outer wall and the floor surface.
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Abstract
Description
本発明の接着剤組成物は、加水分解性シリル基を有するポリアルキレンオキサイドを含有している。ポリアルキレンオキサイドは、ポリアルキレンオキサイド鎖の末端又は側鎖に加水分解性シリル基を有している。ポリアルキレンオキサイド鎖の側鎖に加水分解性シリル基を有しているとは、ポリアルキレンオキサイド鎖に側鎖として加水分解性シリル基を有している場合と、ポリアルキレンオキサイド鎖の側鎖の一部に加水分解性シリル基を有している場合の双方を含む。
測定装置 TOSOH社製 商品名「HLC-8121GPC/HT」
測定条件 カラム:TSKgelGMHHR-H(20)HT×3本
TSKguardcolumn-HHR(30)HT×1本
移動相:o-DCB 1.0mL/分
サンプル濃度:1mg/mL
検出器:ブライス型屈折計
標準物質:ポリスチレン(TOSOH社製 分子量:500~8420000)
溶出条件:145℃
SEC温度:145℃
本発明の接着剤組成物は、エポキシ樹脂を含有している。エポキシ樹脂としては、ビスフェノールAとエピクロロヒドリンとの反応物であるビスフェノールA型エポキシ樹脂、ビスフェノールFとエピクロロヒドリンとの反応物であるビスフェノールF型エポキシ樹脂、これらに水添したエポキシ樹脂;グリシジルエステル型エポキシ樹脂;ノボラック型エポキシ樹脂;ウレタン変性エポキシ樹脂;メタキシレンジやヒダントインなどをエポキシ化した含窒素エポキシ樹脂;ポリブタジエン又はNBR(アクリロニトリル-ブタジエン共重合体)を含有するゴム変性エポキシ樹脂などが挙げられる。なかでも、ビスフェノールA型エポキシ樹脂が好ましい。ビスフェノールA型エポキシ樹脂によれば、接着剤組成物を硬化して得られた接着剤層は、アルカリ性水分の存在にもかかわらず優れた接着強度を維持し且つ寒冷条件下においても優れた接着強度を維持するので好ましい。
本発明の接着剤組成物は、ケチミン化合物を含有している。ケチミン化合物とは、1分子中に2個以上のアミノ基を有しているアミン化合物と、ケトン化合物との脱水縮合物を意味する。ケチミン化合物は潜在性硬化剤として用いられている。ケチミン化合物自体は、水分がない状態では接着剤組成物中でエポキシ樹脂と反応せずに安定的に存在する。しかしながら、ケチミン化合物は、空気中の湿気などの水分と反応して一級アミンとなる。この一級アミンがエポキシ樹脂と反応して接着剤組成物の硬化を促進させることができる。
2,5,8-トリアザ-1,8-ノナジエン、
2,10-ジメチル-3,6,9-トリアザ-2,9-ウンデカジエン、
2,10-ジフェニル-3,6,9-トリアザ-2,9-ウンデカジエン、
3,11-ジメチル-4,7,10-トリアザ-3,10-トリデカジエン、
3,11-ジエチル-4,7,10-トリアザ-3,10-トリデカジエン、
2,4,12,14-テトラメチル-5,8,11-トリアザ-4,11-ペンタデカジエン、
2,4,20,22-テトラメチル-5,12,19-トリアザ-4,19-トリエイコサジエン、及び
2,4,15,17-テトラメチル-5,8,11,14-テトラアザ-4,14-オクタデカジエン。
本発明の接着剤組成物は、脂肪酸処理酸化カルシウムを含んでいる。脂肪酸処理酸化カルシウムを含む接着剤組成物によれば、接着剤組成物を硬化させて得られる接着剤層は、アルカリ性水分の存在にもかかわらず優れた接着強度を維持し且つ寒冷条件下においても優れた接着強度を維持する。
本発明の接着剤組成物は、エポキシシランカップリング剤を含んでいる。エポキシシランカップリング剤とは、一分子中にアルコキシ基が結合した珪素原子と、エポキシ基を有する官能基とを含む化合物を意味する。エポキシシランカップリング剤によれば、アルカリ性水分の存在にもかかわらず優れた接着強度を維持し且つ寒冷条件下においても優れた接着強度を維持する接着剤層を形成することができる。
本発明の接着剤組成物は、シラノール縮合触媒を含有していることが好ましい。シラノール縮合触媒とは、ポリアルキレンオキサイドが有する加水分解性シリル基が加水分解することにより形成されたシラノール基同士の脱水縮合反応を促進させるための触媒である。なお、シラノール基とは、ケイ素原子に直接結合しているヒドロキシ基(≡Si-OH)を意味する。
本発明の接着剤組成物は、必要に応じて、他の添加剤をさらに含んでいてもよい。他の添加剤としては、脱水剤、酸化防止剤、充填材、可塑剤、タレ防止剤、紫外線吸収剤、顔料、溶剤、及び香料などが挙げられる。
本発明の接着剤組成物は、脱水剤をさらに含んでいることが好ましい。脱水剤によれば、接着剤組成物を保存している際に、空気中の湿気などの水分によって接着剤組成物が硬化することを抑制することができる。
本発明の接着剤組成物は、アミノシランカップリング剤をさらに含んでいることが好ましい。アミノシランカップリング剤とは、一分子中にアルコキシ基が結合した珪素原子と、アミノ基を有する官能基とを含む化合物を意味する。アミノシランカップリング剤によれば、エポキシシランカップリング剤と併用することにより、接着剤組成物を硬化させて得られる接着剤層がアルカリ性水分の存在にもかかわらず優れた接着強度を維持し且つ寒冷条件下においても優れた接着強度を維持する。
本発明の接着剤組成物は、酸化防止剤をさらに含有していることが好ましい。酸化防止剤としては、ヒンダードフェノール系酸化防止剤、モノフェノール系酸化防止剤、ビスフェノール系酸化防止剤、及びポリフェノール系酸化防止剤などが挙げられる。なかでも、ヒンダードフェノール系酸化防止剤が好ましい。ヒンダードフェノール系酸化防止剤として、具体的には、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、及びN,N′-ヘキサン-1,6-ジイルビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルプロピオンアミド)]などが挙げられる。酸化防止剤は、一種単独で用いられても二種以上が併用されてもよい。
本発明の接着剤組成物は充填材をさらに含んでいることが好ましい。充填材としては、例えば、炭酸カルシウム、炭酸マグネシウム、含水ケイ酸、無水ケイ酸、ケイ酸カルシウム、シリカ、二酸化チタン、クレー、タルク、カーボンブラック、ガラスバルーン等が挙げられる。充填材は一種単独で用いられてもよく、二種以上が併用されてもよい。
本発明の接着剤組成物は、可塑剤をさらに含んでいることが好ましい。可塑剤を含んでいる接着剤組成物によれば、接着剤組成物を硬化させて得られる接着剤層が寒冷条件下においても優れた接着強度を長期間に亘って維持することができる。
本発明の接着剤組成物は、タレ防止剤を含有していてもよい。タレ防止剤としては、例えば、水添ひまし油、脂肪酸ビスアマイド、ヒュームドシリカ等が挙げられる。
本発明の接着剤組成物は、紫外線吸収剤を含有していてもよい。紫外線吸収剤としては、例えば、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート等のヒンダートアミン系光安定剤、ベンゾトリアゾール系紫外線吸収剤などが挙げられる。
以下に示す成分を、表1~3に示す配合量で配合し、プラネタリーミキサーを用いて真空雰囲気下で60分間混練することにより、接着剤組成物を得た。
・ポリアルキレンオキサイド1(主鎖骨格がポリプロピレンオキサイドからなり、主鎖の末端にジメトキシシリル基を有するポリアルキレンオキサイド、一分子あたりのジメトキシシリル基の平均個数1.4個、数平均分子量20,000、鐘淵化学工業社製 商品名「MSポリマーS-203」)、
・ポリアルキレンオキサイド2(主鎖骨格がポリプロピレンオキサイドからなり、且つ主鎖骨格の両末端にウレタン結合を介してトリメトキシシリル基を有しているポリアルキレンオキサイド、一分子あたりのジメトキシシリル基の平均個数1.8個、数平均分子量13,000、25℃における粘度5,000mPa・s、バイエル社製 商品名「Desmoseal(登録商標)XP2749」)、
・(メタ)アクリレート系重合体(主鎖骨格がメチルメタクリレート-n-ブチルアクリレート共重合体(メチルメタクリレート成分の含有量:25重量%、n-ブチルアクリレート成分の含有量:75重量%)からなり、且つ主鎖骨格の末端又は側鎖にトリメトキシシリル基を有している(メタ)アクリレート系重合体、重量平均分子量3,200、一分子量あたりのトリメトキシシリル基の平均個数0.9、東亞合成株式会社製 アルフォンUS-6110、)、
・エポキシ樹脂1(ビスフェノールA型エポキシ樹脂、エポキシ当量189g/eq、ジャパンエポキシレジン社製 商品名「エピコート828」)、
・エポキシ樹脂2(ビスフェノールF型エポキシ樹脂、エポキシ当量250g/eq、ジャパンエポキシレジン社製 商品名「エピコート806F」)、
・脂肪酸処理酸化カルシウム(オクタデカン酸で表面処理された酸化カルシウム、平均粒子径10μm、近江化学工業社製 商品名「CML#31」)、
・酸化カルシウム(表面処理なし)(近江化学工業社製 商品名「CML#35」)、
・ケチミン化合物(日東化成社製 商品名「エポニットK-100」)、
・シラノール縮合触媒(1,1,3,3-テトラブチル-1,3-ジラウリルオキシカルボニル-ジスタノキサン、日東化成社製 商品名「ネオスタンU-130」)、
・脱水剤(ビニルトリメトキシシラン、日本ユニカ社製 商品名「NUCシリコーンA171」)、
・エポキシシランカップリング剤(3-グリシドキシプロピルトリメトキシシラン、信越化学社製 商品名「KBM-403」)、
・アミノシランカップリング剤(N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、信越化学社製 商品名 KBM-603」)、
・充填材(コロイダル炭酸カルシウム、白石工業社製 商品名「CCR」)、及び
・可塑剤(ポリプロピレングリコール、数平均分子量3000、旭電化社製 商品名「P-3000」)。
JIS A5557に準拠して、硬化性組成物により標準モルタル試験片と磁器製モザイクタイルとを接着一体化させ、標準養生後、アルカリ温水浸漬処理後、又は凍結融解処理後の接着強度を測定した。結果を表1~3に示す。
Claims (4)
- 加水分解性シリル基を有するポリアルキレンオキサイド100重量部、エポキシ樹脂1~20重量部、エポキシシランカップリング剤0.1~10重量部、ケチミン化合物0.5~20重量部、及び脂肪酸処理酸化カルシウム1~100重量部を含有することを特徴とする接着剤組成物。
- エポキシ樹脂が、ビスフェノールA型エポキシ樹脂を含むことを特徴とする請求項1に記載の接着剤組成物。
- アミノシランカップリング剤を更に含有することを特徴とする請求項1又は請求項2に記載の接着剤組成物。
- エポキシ樹脂のエポキシ基の総モル数とケチミン化合物の加水分解物であるアミン化合物が有しているアミノ基の総モル数との比(エポキシ樹脂のエポキシ基の総モル数/ケチミン化合物の加水分解物であるアミン化合物が有しているアミノ基の総モル数)が0.7~1.2であることを特徴とする請求項1~3の何れか1項に記載の接着剤組成物。
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JP2016210826A (ja) * | 2015-04-28 | 2016-12-15 | 積水フーラー株式会社 | 接着剤組成物 |
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JPWO2014200100A1 (ja) | 2017-02-23 |
CN105308145A (zh) | 2016-02-03 |
US20160122606A1 (en) | 2016-05-05 |
JP5636141B1 (ja) | 2014-12-03 |
US9676975B2 (en) | 2017-06-13 |
CN105308145B (zh) | 2018-11-30 |
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