CN101802050A - Microcapsule-type latent curing agent for epoxy resin and process for production thereof, and one-pack-type epoxy resin composition and cured product thereof - Google Patents
Microcapsule-type latent curing agent for epoxy resin and process for production thereof, and one-pack-type epoxy resin composition and cured product thereof Download PDFInfo
- Publication number
- CN101802050A CN101802050A CN200880107917A CN200880107917A CN101802050A CN 101802050 A CN101802050 A CN 101802050A CN 200880107917 A CN200880107917 A CN 200880107917A CN 200880107917 A CN200880107917 A CN 200880107917A CN 101802050 A CN101802050 A CN 101802050A
- Authority
- CN
- China
- Prior art keywords
- microcapsule
- solidifying agent
- type
- epoxy resin
- potentiality solidifying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 179
- 239000003822 epoxy resin Substances 0.000 title claims description 156
- 229920000647 polyepoxide Polymers 0.000 title claims description 156
- 239000000203 mixture Substances 0.000 title claims description 108
- 238000000034 method Methods 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 150000001412 amines Chemical class 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000002775 capsule Substances 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims description 121
- 229920005989 resin Polymers 0.000 claims description 81
- 239000011347 resin Substances 0.000 claims description 81
- 150000002148 esters Chemical class 0.000 claims description 30
- 239000002612 dispersion medium Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012451 post-reaction mixture Substances 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 62
- 238000003860 storage Methods 0.000 description 45
- 239000002245 particle Substances 0.000 description 44
- -1 amine salt Chemical class 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 34
- 239000000843 powder Substances 0.000 description 29
- 238000001723 curing Methods 0.000 description 25
- 229930185605 Bisphenol Natural products 0.000 description 22
- 229940106691 bisphenol a Drugs 0.000 description 22
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 21
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 21
- 238000001816 cooling Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010792 warming Methods 0.000 description 15
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000002966 varnish Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
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- 230000000694 effects Effects 0.000 description 7
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
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- 238000009835 boiling Methods 0.000 description 5
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- 150000002431 hydrogen Chemical class 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 235000019219 chocolate Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
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- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical class C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 2
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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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
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Epoxy Resins (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Disclosed is a microcapsule-type latent curing agent comprising a core and a capsule that sheathes the core. In the microcapsule-type curing agent, the core comprises an amine adduct and the capsule comprises a reaction product of an isocyanate with a compound having an active hydrogen group and/or water. At least a part of the reaction product is bound to the core through the reaction with the amine adduct.
Description
Technical field
The present invention relates to a kind of used for epoxy resin microcapsule-type potentiality solidifying agent and manufacture method and an one-pack-type epoxy resin composition and epoxy resin cured product.
Background technology
For Resins, epoxy,, therefore be used for extensive uses such as coating, electric and electronic insulating material, caking agent because its cured article has excellent performance at aspects such as mechanical characteristics, electrical characteristic, thermal property, resistance to chemical reagents, cementabilities always.Great majority in the present normally used composition epoxy resin are two kinds of liquid, the so-called two fluidity materials of blending epoxy and solidifying agent in use.
Two one-pack-type epoxy resin compositions at room temperature can solidify, and still, Resins, epoxy and solidifying agent must separately be preserved, and as required, must be in weighing, use after mixing both, therefore preserve very complicated with operation.In addition, because work-ing life is limited, therefore macro-mixing in advance, and cooperate frequency gets higher, then can't avoid the decline of efficient.
In order to solve the problem of this two one-pack-type epoxy resin compositions, several one-pack-type epoxy resin compositions have been proposed up to now.The composition that has cooperated potentiality solidifying agent such as Dyhard RU 100 (dicyandiamide), BF3-amine coordination compound, amine salt and modified imidazole mixture in Resins, epoxy is for example arranged.
In addition, also carried out following research, reacted, made the surface inertnessization of amine compound, thereby give potentiality (patent documentation 1～5) solidifying agent by making isocyanic ester and powdered amine compound surface.In addition, thus also proposed to make the powdered amine compound in Resins, epoxy, to react the microcapsule-type solidifying agent (patent documentation 6～8) that makes its capsuleization with isocyanic ester.For example, in patent documentation 6, disclose masterbatch type solidifying agent, that is, will be that solidifying agent is dispersed in the Resins, epoxy as the amine of nuclear, and form the method for shell to wherein adding isocyanic ester and water by following method gained.As other method, it is solidifying agent that blending epoxy and amine are arranged, and freezing immediately make method that reaction stops, with amine be the solidifying agent microencapsulation method, make solidifying agent be adsorbed on method on the molecular sieve.
Patent documentation 1: Japanese Patent Publication 58-55970 communique
Patent documentation 2: Japanese kokai publication sho 59-27914 communique
Patent documentation 3: Japanese kokai publication sho 59-59720 communique
Patent documentation 4: european patent application discloses specification sheets No. 193068
Patent documentation 5: Japanese kokai publication sho 61-190521 communique
Patent documentation 6: Japanese kokai publication hei 1-70523 communique
Patent documentation 7: TOHKEMY 2004-269721 communique
Patent documentation 8: TOHKEMY 2005-344046 communique
Summary of the invention
The problem that invention will solve
Yet, when the potentiality solidifying agent that uses in the past, the material of storage stability excellence, solidified nature is low, needs high temperature or long-time when solidifying.On the other hand, the material that solidified nature is high, then storage stability is low, for example, need store under-20 ℃ of such low temperature.For example, cooperated an one-pack-type epoxy resin composition of Dyhard RU 100, though have the storage stability more than 6 months when normal temperature is preserved, it needs the solidification value more than 170 ℃.If also use curing catalyst in order to reduce this solidification value, can be cured at for example 130 ℃～150 ℃ so.But at this moment, therefore its storage stability deficiency at room temperature must not can only store then at low temperatures, and simultaneously, its work-ing life, (pot life) shortened.Therefore, can't give full play to the potentiality of Dyhard RU 100.Employed composition epoxy resin when making membranaceous moulding product or in base material, flooded the goods of composition epoxy resin, use the compounding ingredient that comprises solvent or reactive diluent etc. mostly, if but in these compounding ingredients, used in the past potentiality solidifying agent, storage stability will be extremely low so.Therefore, in fact compounding ingredient is necessary for two fluidities, and need improve it.
Described as patent documentation 3, the surface functionalities of amine compound is being carried out in the end capped method, as the necessary characteristic of an one-pack-type epoxy resin composition, particularly storage stability aspect, also may not satisfy.In addition, when reality was used an one-pack-type epoxy resin composition, its homogeneity also was very important.Therefore, need usually to use mixing roll devices such as (roll), pulverous solidifying agent is evenly dispersed in the Resins, epoxy.Yet, even use patent documentation 1～4 disclosed any method, because the mechanical shear stress that this scatter operation is at room temperature followed causes the interim inactive surfaces layer that generates destroyed, therefore also has the problem that can't obtain to be enough to carry out practical storage stability.
On the other hand, according to the method for above-mentioned freezing, microencapsulation or molecular sieve, though can obtain better storage stability, present situation is, at aspect of performance, and cured article characteristic aspect deficiency particularly, and almost can't carry out practicability.
As mentioned above, a kind of one-pack-type epoxy resin composition that can make high solidified nature and excellent storage stability and deposit of tight demand.Particularly in recent years, in order to improve,, require further to improve curing characteristics and storage stability for a fluidity resin combination in the productivity aspect the electronic material purposes.
Therefore, the object of the invention is to provide a kind of curability at low temperatures and excellent storage stability and the solidifying agent of depositing and manufacture method thereof that can make an one-pack-type epoxy resin composition.In addition, the object of the invention also is to provide an a kind of one-pack-type epoxy resin composition and cured article thereof that uses solidifying agent of the present invention.
The method of dealing with problems
On the one hand, the present invention relates to have the microcapsule-type potentiality solidifying agent of examining and coating the capsule of this nuclear.In microcapsule-type solidifying agent of the present invention, nuclear comprises amine affixture (amine adduct), and capsule comprises isocyanic ester and the resultant of reaction with compound bearing active hydrogen and/or water.At least a portion of this resultant of reaction is bonded to nuclear by the reaction with the amine affixture.Microcapsule-type solidifying agent of the present invention can be used for cured epoxy resin.Microcapsule-type potentiality solidifying agent of the present invention can be Powdered.
According to the microcapsule-type solidifying agent of the invention described above, can make the curability at low temperatures and the excellent storage stability of an one-pack-type epoxy resin composition and deposit.
In order to make effect of the present invention more remarkable, it is 50～100% amine affixture by quality ratio that above-mentioned nuclear preferably comprises.
Capsular ratio is a benchmark with the total mass of this microcapsule-type potentiality solidifying agent, is preferably 5～80 quality %.Thus, can on higher level, take into account curability at low temperatures and storage stability.
The ratio of capsule also can be 40～80 quality %.Thus, the potentiality solidifying agent can have very good storage stability and solvent resistance.In addition, can also obtain more excellent curability at low temperatures.Therefore, even for example with potentiality solidifying agent and solvent, and when placing for a long time, the nuclear composition of microcapsule-type potentiality solidifying agent can the stripping because of solvent, and can keep its curability at low temperatures.
The ratio of capsule can also be 15～40 quality %.Thus, the potentiality solidifying agent can have better storage stability and solvent resistance, and better curability at low temperatures, and can have these characteristics on very high level simultaneously.Therefore, for example potentiality solidifying agent and Resins, epoxy are being mixed, even and when placing for 1 week under the heated condition about 40 ℃, the reaction of this solidifying agent and Resins, epoxy also can constantly be carried out, thereby viscosity rises, its low-temperature curing characteristic can not lost, and, can show good storage stability and good curability at low temperatures.
The ratio of capsule can also be 5～15 quality %.Thus, the potentiality solidifying agent can have very good curability at low temperatures, and has better storage stability and solvent resistance simultaneously.
On the other hand, the present invention relates to the manufacture method of used for epoxy resin microcapsule-type potentiality solidifying agent.Manufacture method of the present invention comprises amine affixture and isocyanic ester that nuclear is comprised, has compound bearing active hydrogen and/or water reacts in dispersion medium, forms the operation of the capsule that coats nuclear thus.Manufacture method of the present invention further comprises from post reaction mixture, takes out the operation of the pulverous microcapsule-type potentiality solidifying agent with nuclear and capsule.
According to the manufacture method of the invention described above, deviation that can rejection characteristic, and obtain making curability at low temperatures and the excellent storage stability and the microcapsule-type solidifying agent of depositing of an one-pack-type epoxy resin composition.Microcapsule-type potentiality solidifying agent of the present invention can obtain by the manufacture method of the invention described above.
In addition, on the other hand, the present invention relates to an a kind of one-pack-type epoxy resin composition.An one-pack-type epoxy resin composition of the present invention contains the used for epoxy resin microcapsule-type potentiality solidifying agent and the Resins, epoxy of the invention described above.
An one-pack-type epoxy resin composition of the present invention has curability at low temperatures and excellent storage stability.
Used for epoxy resin microcapsule-type potentiality solidifying agent can carry out heat treated in Resins, epoxy.An one-pack-type epoxy resin composition of the present invention with respect to total amount 100 mass parts of Resins, epoxy and microcapsule-type potentiality solidifying agent, preferably contains 5～70 mass parts microcapsule-type potentiality solidifying agent.
Further, on the other hand, the present invention relates to a kind of cured article of composition epoxy resin.Cured article of the present invention is by heating one one-pack-type epoxy resin composition of the invention described above to be solidified to form.Cured article of the present invention, excellent especially aspect electrical specification (insulativity).
The invention effect
According to microcapsule-type curing agent of the present invention, can make the curability at low temperatures and the excellent storage stability of an one-pack-type epoxy resin composition and deposit.Therefore, microcapsule-type curing agent of the present invention has improved productivity at aspects such as electronic material purposes, thus preferred the use.
Powdered microcapsule-type potentiality solidifying agent of the present invention in the following areas, has excellent action effect.
(1) owing to be Powdered, therefore can consider the rerum natura of its curing characteristics and cured article etc.,, at an easy rate it is dispersed in the Resins, epoxy according to purpose.In addition, the degree of freedom of the proportioning of solidifying agent is also very high in the composition epoxy resin.
(2) owing to can control the capsule part at an easy rate, therefore can obtain to have the potentiality solidifying agent of good solidification characteristic and good storage stability at an easy rate according to purpose.
(3) owing to can make an one-pack-type epoxy resin composition at an easy rate, therefore can improve the operability when using, and obtain the high reliability of goods.
Microcapsule-type potentiality solidifying agent of the present invention also has following action effect: even applied mechanical shear stress when preparation one one-pack-type epoxy resin composition, performance variation is also very little.
Manufacturing method according to the invention, deviation that can rejection characteristic, and obtain taking into account the microcapsule-type solidifying agent of the curability at low temperatures and the excellent storage stability of an one-pack-type epoxy resin composition.Make the powdered amine compound in Resins, epoxy with the manufacture method in the past of isocyanate reaction in, for example, in order to improve curability at low temperatures, and increase the amount of microcapsule-type potentiality solidifying agent, therefore need in Resins, epoxy, add a large amount of powdered amine compounds.When the quantitative change of powdered amine compound for a long time, viscosity uprises, and therefore is difficult to carry out uniform capsule reaction.As a result, it is big that the characteristic deviation between different batches becomes, and the disqualification rate of goods uprises, and forms the degree deficiency of capsule, can not get enough storage stabilities.In addition, if in order to improve curing characteristics, and use reactive high composition with Resins, epoxy as nuclear matter, so also there are the following problems: since in Resins, epoxy the carrying out of curing reaction, so can not synthesize potentiality solidifying agent with abundant characteristic.Manufacturing method according to the invention owing to nuclear and the reaction of Resins, epoxy and the reaction of isocyanic ester, water and Resins, epoxy that can suppress to cause viscosity rising reason, therefore can obtain a mobile high one-pack-type epoxy resin.Consider that from these viewpoints manufacture method of the present invention is compared with method in the past, has favourable effect.
Manufacture method according to microcapsule-type potentiality solidifying agent of the present invention, behind the powdered amine compound that in Resins, epoxy, cooperates as solidifying agent, the method that forms shell is compared, and reduces because curing reaction and viscosity rise, therefore can be more easily, react equably.Therefore, the characteristic deviation between different batches diminishes.In addition, also remove by product easily.Further, owing to do not need to distinguish solidifying agent according to the kind of each Resins, epoxy that makes up, therefore, operation efficiency is good, and the range of choice of Resins, epoxy is wide.
The viscosity height of masterbatch type solidifying agent in the past is difficult to realize enough flowabilities of composition epoxy resin, but according to the present invention, can obtains having an one-pack-type epoxy resin composition of enough high workabilities.In recent years, particularly in the e-machine field,, can be used as an one-pack-type epoxy resin composition that connects one of material for the densification of tackling circuit and the raising of connection reliability, need fill between narrow and small slit, therefore having high workability becomes more important.
In Resins, epoxy, add isocyanic ester and water, thereby in powdered amine is to form on the surface of solidifying agent in the method for shell, be easy to generate the side reaction of primary amine and Resins, epoxy reaction, described primary amine is by being generated as the isocyanic ester of side reaction and the reaction of water, therefore, be difficult to obtain the reproducibility of resultant.In addition, because solidifying agent is with resulting with the state of the title complex (masterbatch) of specific Resins, epoxy, therefore also have the problem that cooperates degree of freedom to be restricted.The present invention also is favourable on addressing these problems.
Owing to produced above these effects, so a microcapsule-type potentiality solidifying agent of the present invention and an one-pack-type epoxy resin composition can use in the purposes field widely.For example, an one-pack-type epoxy resin composition of the present invention can be used as caking agent, in automotive field, be used for headlight, fuel tank bonding, dogleg section such as engine shield bonding, the joint of vehicle body and top of car steel plate, in electric field, be used for the bonding of speaker magnets, the dipping of engine coil and bonding, magnetic head, cell box bonding, luminescent lamp stabilizer bonding, in electronic applications, be used for wafer joint caking agent, IC chip sealing agent, the chip coating material, the chip installing material, the caking agent of printing element, the film caking agent, anisotropic conductive film, purposes such as anisotropic conductive paste.As other purposes, in paint field, can enumerate powder coating, welding resistance printing ink, conductive coating paint etc.In addition, in insulating material, laminated structure etc., also can utilize the present invention.Particularly in recent years, in order to improve,, require further to improve curing characteristics and storage stability for a fluidity resin combination in the productivity aspect the electronic material purposes.
The best mode that is used to carry out an invention
Below, preferred implementation of the present invention is elaborated.But the present invention is not limited to following embodiment.
The microcapsule-type potentiality solidifying agent of present embodiment, the capsule that has emboliform nuclear and coat this nuclear.Capsule is the film that coats at least a portion on nuclear surface.
Nuclear comprises the amine affixture as principal constituent.More particularly, it is 50～100% by quality ratio that nuclear comprises usually, is preferably 60～100% amine affixture.When the mass ratio of amine affixture less than 50% the time, have and make the relatively tendency of difficulty of curing characteristics and storage stability coexistence.
The amine affixture is the compound reaction gained, that have amino by Resins, epoxy and amine compound.
As the Resins, epoxy that is used to obtain the amine affixture, can use any of mono-epoxy compounds and polynary epoxy compounds, perhaps their mixture.As mono-epoxy compounds, for example, butylglycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, glycidyl allyl ether, to tert-butyl-phenyl glycidyl ether, oxyethane, propylene oxide, p-Xylol base glycidyl ether, acetate glycidyl ester, Glycidyl butyrate, caproic acid glycidyl ester and phenylformic acid glycidyl ester etc.As polynary epoxy compounds, bisphenols such as the dihydroxyphenyl propane of can giving an example, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, tetrabromo-bisphenol, tetrachlorobisphenol A, tetrafluoro dihydroxyphenyl propane are through the bisphenol-type epoxy resin of glycidyl gained; Xenol, dihydroxy naphthlene, 9, other dihydric phenols such as two (4-hydroxy phenyl) fluorenes of 9-are through the Resins, epoxy of glycidyl gained; 1,1,1-three (4-hydroxy phenyl) methane, 4, three phenols such as 4-(1-(4-(1-(4-hydroxy phenyl)-1-methylethyl) phenyl) ethylidene) bis-phenol are through the Resins, epoxy of glycidyl gained; 1,1,2, four phenols such as 2-four (4-hydroxy phenyl) ethane are through the Resins, epoxy of glycidyl gained; Phenolic varnish classes such as phenol phenolic varnish, cresols phenolic varnish, bisphenol-A phenolic varnish, bromination phenol phenolic varnish, brominated bisphenol A phenolic varnish are through the phenolic resin varnish type epoxy resin of glycidyl gained; Polyatomic phenol is through the polyvalent alcohols such as Resins, epoxy, glycerol or polyoxyethylene glycol of the glycidyl gained aliphatics ether type epoxy through the glycidyl gained; Hydroxycarboxylic acid such as P-hydroxybenzoic acid, β-Qiang Jinaijiasuan is through the ether ester epoxy resin of glycidyl gained; The such polycarboxylic acid of phthalic acid, terephthalic acid is through the ester type epoxy resin of glycidyl gained; 4, the glycidyl thing of amine compound such as 4-diaminodiphenyl-methane or Metha Amino Phenon, or Racemic glycidol fundamental mode Resins, epoxy, 3 such as amine type Resins, epoxy such as triglycidyl group isocyanuric acid ester, 4-epoxy group(ing) cyclohexyl methyl-3 ', cycloaliphatic epoxides such as 4 '-epoxy-cyclohexane carboxylicesters.
As Resins, epoxy, consider from the viewpoint of the storage stability that can improve composition epoxy resin, be preferably polynary Resins, epoxy.As polynary Resins, epoxy,, therefore be preferably Racemic glycidol fundamental mode Resins, epoxy because the productivity absoluteness of amine compound ground is high.Consider that from the viewpoint of the cementability of cured article and excellent heat resistance polynary epoxy compounds is the glycidyl thing of polyatomic phenol more preferably, and bisphenol-type epoxy resin more preferably.Especially, preferably as the bisphenol A type epoxy resin of dihydroxyphenyl propane, and as the bisphenol f type epoxy resin of Bisphenol F through the Resins, epoxy of glycidylization through the Resins, epoxy of glycidylization, and bisphenol A type epoxy resin most preferably wherein.These Resins, epoxy may be used alone, can also be used in combination.
Be used to obtain the amine compound of amine affixture, be preferably selected from and have primary amino and/or secondary amino group but do not have the compound of uncle's amino and have uncle's amino and compound bearing active hydrogen.As having primary amino and/or secondary amino group but do not have the compound of uncle's amino, for example, can enumerate methylamine, ethamine, propylamine, butylamine, quadrol, propylene diamine, hexanediamine, Diethylenetriamine, three second tetramines, thanomin, Propanolamine, hexahydroaniline, isophorone diamine, aniline, Tolylamine, diaminodiphenyl-methane, with primary amine classes such as diaminodiphenylsulfone(DDS)s, and dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexyl amine, piperidines, piperidone, diphenylamine, secondary amine classes such as phenyl methyl amine and phenyl ethyl amine.
In having uncle's amino and compound bearing active hydrogen, as active hydrogen, can give an example primary amino, secondary amino group, hydroxyl, sulfydryl, carboxylic acid and hydrazide group.As having uncle's amino and compound bearing active hydrogen, for example, can enumerate alkamines such as 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-DEAE diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, trolamine and N-beta-hydroxyethyl morpholine; 2-(dimethylaminomethyl) phenol and 2,4, aminophenols such as 6-three (dimethylaminomethyl) phenol; Glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole, 1-amino-ethyl-glyoxal ethyline, 1-(2-hydroxyl-3-phenoxy propyl)-glyoxal ethyline, 1-(2-hydroxyl)-3-phenoxy propyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxyl-3-butoxy propyl group)-glyoxal ethyline and 1-(2-hydroxyl-3-butoxy propyl group)-imidazoles such as 2-ethyl-4-methylimidazole; 1-(2-hydroxyl-3-phenoxy propyl)-2-benzylimidazoline, 1-(2-hydroxyl-3-butoxy propyl group)-glyoxal ethyline quinoline, the glyoxal ethyline quinoline, 2,4-methylimidazole quinoline, 2-ethyl imidazol(e) quinoline, the 2-ethyl-4-methylimidazole quinoline, the 2-benzyl imidazoline, the 2-benzylimidazoline, 2-(o-tolyl)-tetrahydroglyoxaline, tetramethylene-two-tetrahydroglyoxaline, 1,1,3-trimethylammonium-1,4-tetramethylene-two-tetrahydroglyoxaline, 1,3,3-trimethylammonium-1,4-tetramethylene-two-tetrahydroglyoxaline, 1,1,3-trimethylammonium-1,4-tetramethylene-two-4-methylimidazole quinoline, 1,2-phenylene-two-tetrahydroglyoxaline, 1,3-phenylene-two-tetrahydroglyoxaline, 1,4-phenylene-two-tetrahydroglyoxaline, 1,4-phenylene-two-imidazolines such as 4-methylimidazole quinoline; The amino amines of uncle such as dimethylamino propylamine, diethyl amino propylamine, the amino propylamine of dipropyl, dibutyl amino propyl amine, dimethylamino ethamine, diethylamino ethamine, dipropyl aminoethyl, dibutylamino ethamine, N methyl piperazine, N-aminoethyl piperazine and diethylamino ethyl piperazidine; Amineothiot classes such as 2-dimethylamino sulfur alcohol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine and 4-mercaptopyridine; N, N-dimethylaminobenzoic acid, N, aminocarboxylic acids such as N-N-methylsarcosine, nicotinic acid, Yi Yansuan, picolinic acid; N, amino hydrazides classes such as N-N-methylsarcosine hydrazides, hydroxyacyl hydroxyacyl hydrazine and isonicotinic acid hydrazide.
As amine compound, consider preferably have uncle's amino and compound bearing active hydrogen from the viewpoint of the balance excellence of storage stability and solidified nature.Wherein, more preferably imidazoles, and further preferred glyoxal ethyline and 2-ethyl-4-methylimidazole.
Nuclear except the amine affixture, can also contain other composition more than a kind or 2 kinds.By adding other composition, can give desirable characteristic.For example, in order can or to solidify in the shorter time under low temperature more, can contain compound or the curing catalyst higher than amine affixture in the nuclear with the reactivity of Resins, epoxy.Can also in nuclear, add needed additive in the cured article in advance.
This other composition wishes that it is solid state down at normal temperature (25 ℃).Preferably be solid state down, and more preferably be solid state down at 60 ℃ at 40 ℃.If use at normal temperatures, then be difficult to capsuleization, and have the tendency that the storage stability of an one-pack-type epoxy resin composition descends to the composition of liquid.
Amine affixture and other composition, preferably uniform mixing in nuclear.As realizing mixed uniformly method, have amine affixture and other composition heating and melting together, and behind thorough mixing, be cooled to the method that normal temperature is pulverized, and heating and melting is wherein a kind of, again another kind is dispersed in wherein, forms the homodisperse thing, and be cooled to the method that normal temperature is pulverized.
Nuclear is preferably the particle shape with 0.1～50 μ m median size.Median size 0.5～10 μ m more preferably of nuclear, and 0.5～5 μ m more preferably.When the median size of nuclear during, have tendency solidified nature and storage stability and that deposit the comparison difficulty less than 0.1 μ m.In addition, be below the 50 μ m as the median size of fruit stone, then obtain the cured article of homogeneous easily.Above-mentioned median size is meant median particle diameter.The median size of nuclear can be measured by laser diffraction formula particle size distribution device.
The shape of nuclear is not particularly limited, can be spherical or unbodied any, but, be preferably spherical for the lowering viscousity of an one-pack-type epoxy resin composition., spherically not only comprise positive spheroid herein, comprise that also unbodied angle is to have circular shape.
Microcapsule-type potentiality solidifying agent, for example, can obtain by following manufacture method, this manufacture method comprises amine affixture and isocyanic ester that nuclear is comprised, have compound bearing active hydrogen and/or water reacts in dispersion medium, form the capsular operation that coats nuclear thus, and from post reaction mixture, take out operation with nuclear and capsular microcapsule-type curing agent.
Isocyanic ester is to have 1 above isocyanate group, and is preferably the compound of 2 above isocyanate group.As preferred isocyanic ester, can enumerate aliphatic diisocyanate, ester ring type vulcabond, aromatic diisocyanate, low molecule triisocyanate and polyisocyanates.As the example of aliphatic diisocyanate, can enumerate ethylidene diisocyanate, trimethylene diisocyanate, butylidene vulcabond, hexamethylene diisocyanate and trimethyl hexamethylene diisocyanate etc.Example as the ester ring type vulcabond, can enumerate isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, norbornene alkyl diisocyanate, 1,4-isocyanate group hexanaphthene, 1,3-two (isocyanic ester ylmethyl)-hexanaphthene, 1,3-two (2-isocyanate group propyl group-2-yl)-hexanaphthene etc.As the example of aromatic diisocyanate, can enumerate tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, diformazan phenylene diisocyanate and 1,5-naphthalene diisocyanate.Example as low molecule triisocyanate, can enumerate 1,6,11-undecane triisocyanate, 1,8-is diisocyanate based-4-isocyanate group methyloctane, 1,3,6-hexa-methylene triisocyanate, 2,6-two isocyanato-s caproic acid-2-isocyanatoethyl, 2, the diisocyanate based caproic acid of 6--1-methyl-aliphatics triisocyanate compounds such as 2-ethyl isocyanate, ester ring type triisocyanate compounds such as thricyclohexyl methane triisocyanate and bicycloheptane triisocyanate, triphenylmethane triisocyanate, aromatic series triisocyanate compounds such as three (isocyanate group phenyl) thiophosphatephosphorothioate.As polyisocyanates, the poly methylene poly phenyl poly isocyanate of can giving an example, or by above-mentioned vulcabond, low molecule triisocyanate deutero-polyisocyanates.As by above-mentioned vulcabond, triisocyanate deutero-polyisocyanates, isocyanuric acid ester type polyisocyanates, biuret type polyisocyanates, ammonia ester type polyisocyanates, allophanate type polyisocyanates, carbodiimide type polyisocyanates etc. are arranged.These isocyanic ester can use separately, or use more than 2 kinds.
The active hydrogen that is had by the amine affixture and the reaction of isocyanic ester, amine affixture and isocyanic ester combination, and on the nuclear surface, form coating film by resultant.So, having compound bearing active hydrogen and/or water is present in the reaction system by making, the coating film that contains the resultant of reaction of they and isocyanic ester is constantly grown, and forms capsule.At least a portion of contained resultant of reaction is bonded to nuclear by the ammonia ester bond that reaction generated of isocyanic ester and amine affixture in the capsule.By using the coating film microcapsule-type potentiality solidifying agent of growth like this, can think the enough storage stabilities that obtained an one-pack-type epoxy resin composition.
In microcapsule-type potentiality solidifying agent, the ratio of capsule (inert coating) is a benchmark with the total mass of microcapsule-type potentiality solidifying agent, is preferably 5～80 quality %.The ratio of capsule according to desirable purposes or purpose etc., also can be 40～80 quality %, 15～40 quality % or 5～15 quality %.
The ratio of capsule, for example, can obtain by this method, promptly, the microcapsule-type potentiality solidifying agent of mass M 1 is dispersed in the solvent of selective dissolution nuclear part, measure the mass M 2 of undissolved solids component at this moment, and by following formula: the ratio of capsule (quality %)=(M2/M1) * 100 is calculated the ratio of capsule.Solvent as selective dissolution nuclear for example, can use methyl alcohol.
As the active hydrogen of the compound that is used to form capsule, can give an example primary amino, secondary amino group, hydroxyl, sulfydryl, carboxylic acid and hydrazide group.Having 1 above compound bearing active hydrogen in 1 molecule can use, and preferably uses to have 2 above compound bearing active hydrogen in 1 molecule.Have 2 above compound bearing active hydrogen by use, the coating film on nuclear surface is grown up efficiently, thereby can make the excellent especially microcapsule-type potentiality solidifying agent of storage stability.Have compound bearing active hydrogen, can use a kind separately, perhaps will be used in combination more than 2 kinds.
Form the reaction of capsule, can in the reaction solution that nuclear is dispersed in the dispersion medium, carry out.Reaction is preferably carried out under fusing point that constitutes the composition of examining (particularly amine affixture) or the temperature below the softening temperature.
The boiling point of dispersion medium is below 150 ℃ under 1 normal atmosphere preferably.If the boiling point of dispersion medium is more than 150 ℃, then have the tendency that is difficult to from reaction solution, remove dispersion medium.In addition, the viscosity of dispersion medium is down below the 1000mPas at 25 ℃ preferably.If the viscosity of dispersion medium is more than the 1000mPas, then be difficult to react uniformly, therefore there is the aggegation of rewarding microcapsule-type potentiality solidifying agent, and the remarkable possibility that descends of curing characteristics.By same viewpoint as can be known, more preferably, the boiling point of dispersion medium is 50～120 ℃, and the viscosity of dispersion medium is 0.2～10mPas.
Dispersion medium preferably do not have active hydrogen, with the substituting groups such as epoxy group(ing) of amine affixture reaction.These substituting groups have and hinder the possibility that capsule forms reaction.As the object lesson of suitable dispersion medium, can enumerate hexanaphthene (boiling point is 80.7 ℃, and viscosity is 0.898mPas:25 ℃) and hexane (boiling point is 69 ℃, and viscosity is 0.299mPas:25 ℃).
After forming capsule, from the mixture that contains microcapsule-type potentiality solidifying agent and dispersion medium etc., remove dispersion medium.When remaining when unreacted isocyanic ester, by product, water being arranged and/or having compound bearing active hydrogen in the dispersion medium,, can separate in the remnant of microcapsule-type potentiality solidifying agent from dispersion medium and take out by removing dispersion medium.When unreacted reactant is included in the microcapsule-type potentiality solidifying agent, have the possibility that storage stability descends.
The method of removing of dispersion medium is not particularly limited, preferably with unreacted isocyanic ester, by product, water with have remnants such as compound bearing active hydrogen and remove with dispersion medium.As preferable methods, can enumerate filtration.Preferably after removing dispersion medium, wash microcapsule-type potentiality solidifying agent by filtration etc.The method of washing is not particularly limited, and can use the solvent that does not dissolve microcapsule-type potentiality solidifying agent to wash after filtration.As this solvent, can use the material identical with dispersion medium.By washing, can remove attached to unreacted compound on the microcapsule-type potentiality solidifying agent surface.Microcapsule-type potentiality solidifying agent after filtering forms Powdered by drying.The exsiccant method is not particularly limited, but preferably carries out drying under fusing point of examining or the temperature below the softening temperature.As this method, can enumerate drying under reduced pressure.Because pulverous microcapsule-type solidifying agent can carry out various cooperations in an one-pack-type epoxy resin composition, can use at an easy rate.
When use is carried out the method for capsuleization in Resins, epoxy, unreacted isocyanic ester and by product, water and/or have compound bearing active hydrogen and remain in the one-pack-type epoxy resin composition, storage stability will descend as a result.In addition, when being added in Resins, epoxy with high density pulverous amine affixture particle, viscosity significantly uprises, and can't react uniformly, and the property difference between different batches becomes big, also can produce capsule reaction itself and problem such as can't carry out.In order to improve reactivity, if use the nuclear added with the reactive high compound of Resins, epoxy, and use reactive high Resins, epoxy as dispersion medium, carry out capsuleization, the reaction of nuclear and Resins, epoxy is preferentially carried out so, is difficult to make a microcapsule-type potentiality solidifying agent or an one-pack-type epoxy resin composition.
Form the reaction of capsule, if necessary, can carry out more than 2 times.At this moment, the reaction that at least once carry out amine affixture, isocyanic ester, has compound bearing active hydrogen and/or water gets final product, and any that in addition, can also use and be selected from isocyanic ester, have compound bearing active hydrogen and/or water reacts.Consider that from the viewpoint that suppresses manufacturing cost the reaction that forms capsule is preferably below 5 times, and more preferably below 3 times.
One-pack-type epoxy resin composition in the present embodiment contains microcapsule-type potentiality solidifying agent and Resins, epoxy.The amount of microcapsule-type potentiality solidifying agent is not particularly limited, and with respect to total amount 100 mass parts of Resins, epoxy and microcapsule-type potentiality solidifying agent, is about 5～70 mass parts usually.If should amount less than 5 weight parts, then have Resins, epoxy and be difficult to abundant solidified tendency, perhaps having needs tendency for a long time when solidifying, and if it surpasses 70 mass parts, then have the tendency that the flowability of composition epoxy resin descends.
As Resins, epoxy used in the one-pack-type epoxy resin composition, can preferably use epoxy compounds with average 2 above epoxy group(ing).Specifically, bisphenols such as dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, tetrabromo-bisphenol, tetrachlorobisphenol A and tetrafluoro dihydroxyphenyl propane are through the bisphenol-type epoxy resin of glycidyl gained; Xenol, dihydroxy naphthlene and 9, other dihydric phenols such as two (4-hydroxy phenyl) fluorenes of 9-are through the Resins, epoxy of glycidyl gained; 1,1,1-three (4-hydroxy phenyl) methane and 4, three phenols such as 4-(1-(4-(1-(4-hydroxy phenyl)-1-methylethyl) phenyl) ethylidene) bis-phenol are through the Resins, epoxy of glycidyl gained; 1,1,2, four phenols such as 2-four (4-hydroxy phenyl) ethane are through the Resins, epoxy of glycidyl gained; Phenolic varnish classes such as phenol phenolic varnish, cresols phenolic varnish, bisphenol-A phenolic varnish, bromination phenol phenolic varnish and brominated bisphenol A phenolic varnish are through the phenolic resin varnish type epoxy resin of glycidyl gained; Polyatomic phenol is through the polyvalent alcohols such as Resins, epoxy, glycerol or polyoxyethylene glycol of the glycidyl gained aliphatics ether type epoxy through the glycidyl gained; Hydroxycarboxylic acid such as P-hydroxybenzoic acid, β-Qiang Jinaijiasuan is through the ether ester epoxy resin of glycidyl gained; The such polycarboxylic acid of phthalic acid, terephthalic acid is through the ester type epoxy resin of glycidyl gained; 4, the glycidyl thing of amine compound such as 4-diaminodiphenyl-methane or Metha Amino Phenon, or Racemic glycidol fundamental mode Resins, epoxy, 3 such as amine type Resins, epoxy such as triglycidyl group isocyanuric acid ester, 4-epoxy group(ing) cyclohexyl methyl-3 ', cycloaliphatic epoxides such as 4 '-epoxy-cyclohexane carboxylicesters.As other example of Resins, epoxy, modified epoxies such as the ester modified Resins, epoxy of ammonia, rubber modified epoxy resin, alkyd modified Resins, epoxy are arranged.These Resins, epoxy can use separately, also can will be used in combination more than 2 kinds.
One one-pack-type epoxy resin composition except microcapsule-type potentiality solidifying agent, can also further contain at least a solidifying agent that is selected from anhydrides, phenols, hydrazides class and guanidine class.And an one-pack-type epoxy resin composition can also contain extender, supporting material, packing material, electrically conductive particles, pigment, organic solvent, reactive diluent, non-reactive diluent, resene, crystallinity alcohol, coupling agent etc. as required.
Example as weighting agent, for example, can enumerate coal tar, glass fibre, fibrous magnesium silicate, boron fibre, carbon fiber, Mierocrystalline cellulose, the polyethylene powder, polypropylene powder, silica powder, mineral silicate, mica, asbestos powder, slate flour, kaolin, hibbsite, aluminium hydroxide, whiting, gypsum, lime carbonate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, penton, silicon-dioxide, aerosol, lithopone, barite, titanium dioxide, carbon black, graphite, carbon nanotube, soccerballene, ferric oxide, gold, silver, aluminium powder, iron powder, the metallic crystal of nano-scale, intermetallic compound etc.They can effectively use according to purposes.
Example as electrically conductive particles, can enumerate, for example the metallic crystal of scolding tin particle, nickel particles, nano-scale, metallic surface are by the metallicss such as gradient particle of other plated particle, copper and silver, perhaps use conductive membranes such as gold, nickel, silver, copper, scolding tin, for example resin particles such as styrene resin, ammonia ester resin, melamine resin, Resins, epoxy, acrylic resin, resol, styrene butadiene resin have been implemented the particle of covering etc.
As organic solvent, for example, can enumerate toluene, dimethylbenzene, methylethylketone, hexone, ethyl acetate and butylacetate.
As reactive diluent, for example, can enumerate butylglycidyl ether, N, N '-glycidyl-Ortho Toluidine, phenyl glycidyl ether, Styrene oxide 98min., ethylene glycol diglycidylether, propylene glycol diglycidylether and 1,6-hexanediol diglycidyl ether.As non-reactive diluent, for example, can enumerate dioctyl phthalate (DOP), dibutyl phthalate, Octyl adipate and oil series solvent.
As resene, for example, can enumerate vibrin, urethane resin, acrylic resin, polyether resin, melamine resin and phenoxy resin.
As crystallinity alcohol, for example, can enumerate 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, tetramethylolmethane, Sorbitol Powder, sucrose and TriMethylolPropane(TMP).
One one-pack-type epoxy resin composition, preferably can obtain by following manufacture method, this manufacture method is included in the mixture of microcapsule-type potentiality solidifying agent and Resins, epoxy mixing gained and makes microcapsule-type potentiality solidifying agent carry out the dispersive operation, and the operation of the microcapsule-type potentiality solidifying agent after disperseing being carried out heat treated.
By using mixing machine or mixing roll etc. to stir the mixture of microcapsule-type potentiality solidifying agent and Resins, epoxy, microcapsule-type potentiality solidifying agent can be dispersed in the Resins, epoxy.
By the microcapsule-type potentiality solidifying agent in the Resins, epoxy is carried out heat treated, can make Resins, epoxy enter into capsule, thereby further improve storage stability.The temperature of heat treated, preferably than normal temperature (25 ℃) height, and for the fusing point of the amine affixture that constitutes nuclear or below the softening temperature.Be lower than under the temperature of normal temperature, having storage stability and improve the tendency that effect diminishes, and under the temperature of fusing point that is higher than the amine affixture or softening temperature, owing to the reaction with Resins, epoxy causes the characteristic of solidifying agent to descend easily.Treatment time is 5 minutes to 72 hours, considers it is preferred from productive viewpoint.
One-pack-type epoxy resin composition in the present embodiment solidifies by heating, and forms cured article.A this one-pack-type epoxy resin composition, use thickener, joint with the film except being used as caking agent and/or engaging, can also be used as electro-conductive material, anisotropic conductive material, insulating material, sealing material, coating material, coating composition, prepreg, thermally-conductive materials etc.
Embodiment
Below, enumerate embodiment, the present invention is carried out more specific description.But the present invention is not limited thereto.
(research 1)
1-1. amine affixture particle is synthetic
Amine affixture particle 1
In having the detachable there-necked flask of 3000ml of cooling tube, isobaric dropping funnel, whipping appts, the glyoxal ethyline that in the solution that mixes 1-butanols and toluene gained with 1/1 (wt/wt) of 824.2g, adds 288g, in oil bath, be heated to 80 ℃ while stirring, make the glyoxal ethyline fusion.Then, use isobaric dropping funnel, in 90 minutes, splash into following solution, described solution is that the bisphenol A type epoxy resin of 946g (epoxy equivalent (weight) is 173g/eq, and hydrolyzable chloride content is 0.01 weight %) is dissolved in 300g with resulting solution in the mixed solvent of 1/1 (wt/wt) mixing 1-butanols and toluene gained.After splashing into end, heated 5 hours down at 80 ℃.Then, be warming up to 180 ℃, and to be decompressed to resulting pressure in will installing be below the 10mmHg.After pressure reaches below the 10mmHg, further, heat up in a steamer and desolvate by under reduced pressure heating 2 hours, obtain the thick liquid of chocolate.This thick liquid is cooled to room temperature, obtains the solid state amine affixture of chocolate.Use jet mill to pulverize this amine affixture, obtaining median size is the amine affixture particle 1 of 1.96 μ m.
Amine affixture particle 2
Except bisphenol A type epoxy resin being changed into outside the 874g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and hydrolyzable chloride content is 0.007 weight %), use the method identical with amine affixture 1, obtaining median size is the amine affixture particle 2 of 1.88 μ m.
1-2. microcapsule-type potentiality solidifying agent is synthetic
Microcapsule-type potentiality solidifying agent 1
In the detachable there-necked flask of the 500mL with cooling tube, thermopair, whipping appts, add 45.0g amine affixture particle 1 and 171.0g hexanaphthene, and after being heated to 40 ℃, add 1.2g water.Stir after 10 minutes, add 3.0g 4,4 '-diphenylmethanediisocyanate makes it react 2 hours down at 40 ℃.Then, be warming up to 50 ℃, reacted 6 hours.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ hexanaphthene washing and recycling.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains microcapsule-type potentiality solidifying agent 1.
Microcapsule-type potentiality solidifying agent 2
Except use amine affixture 2 to replace the amine affixtures 1 and embodiment 1 same, obtain microcapsule-type potentiality solidifying agent 2.
Microcapsule-type potentiality solidifying agent 3 (capsuleization again of microcapsule-type potentiality solidifying agent 1)
In the detachable there-necked flask of the 500mL with cooling tube, thermopair, whipping appts, add 146.3g toluene and 2.5g 4,4 '-diphenylmethanediisocyanate, and in oil bath, be heated to 50 ℃.Then, add 15.0g microcapsule-type potentiality solidifying agent (F) 1, reacted 3 hours down at 50 ℃.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ toluene wash recovery.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains microcapsule-type potentiality solidifying agent 3.
Microcapsule-type potentiality solidifying agent 4 (interpolation ethylene glycol)
In the detachable there-necked flask of the 500mL with cooling tube, thermopair, whipping appts, add 45.0g amine affixture 1 and 171.0g hexanaphthene, and be heated to 40 ℃.Then, add the 2.0g tolylene diisocyanate, heated 2 hours down at 40 ℃.Further be warming up to 50 ℃, and added 3.0g ethylene glycol through 6 hours.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ hexanaphthene washing and recycling.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains microcapsule-type potentiality solidifying agent 4.
Microcapsule-type potentiality solidifying agent 6
In the detachable there-necked flask of the 500mL with cooling tube, thermopair, whipping appts, add 45.0g amine affixture particle 1 and 171.0g hexanaphthene, and be heated to 40 ℃, add 1.2g water then.Stir after 10 minutes, add 3.0g polymeric MDI (Japanese polyurethane society (Japanese Port リ ウ レ タ Application society) and make trade(brand)name: Mi Lveleite MR-200 (ミ リ オ ネ one ト MR-200)), 40 ℃ of reactions 2 hours down.Then, be warming up to 50 ℃, reacted 6 hours.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ hexanaphthene washing and recycling.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains microcapsule-type potentiality solidifying agent 6.
1-3. the modulation of an one-pack-type epoxy resin composition
Embodiment 1～3
Cooperate 33g microcapsule-type potentiality solidifying agent 1,2 or 3 and 67g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and hydrolyzable chloride content is 0.007 weight %), obtain the one-pack-type epoxy resin composition of embodiment 1～3.
Embodiment 4
Cooperate 33g microcapsule-type potentiality solidifying agent 4 and 67g bisphenol A type epoxy resin (epoxy equivalent (weight) is 173g/eq, and hydrolyzable chloride content is 0.01 weight %), obtain an one-pack-type epoxy resin composition.
Embodiment 5
Cooperate 45g microcapsule-type potentiality solidifying agent 3 and 55g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and hydrolyzable chloride content is 0.007 weight %), obtain an one-pack-type epoxy resin composition.
Embodiment 6
Cooperate 35g microcapsule-type potentiality solidifying agent 3, (epoxy equivalent (weight) is 160g/eq to the 25g bisphenol A type epoxy resin, hydrolyzable chloride content is 0.007 weight %) and the 40g resorcinol diglycidyl ether (epoxy equivalent (weight) is 117g/eq, hydrolyzable chloride content is 0.7 weight %), obtain an one-pack-type epoxy resin composition.
Embodiment 7
33g microcapsule-type potentiality solidifying agent 1 joined have cooling tube, in the detachable there-necked flask of thermopair, whipping appts, and (epoxy equivalent (weight) is 160g/eq to add the 67g bisphenol f type epoxy resin, hydrolyzable chloride content is 0.007 weight %), stirred 24 hours down at 50 ℃, obtain an one-pack-type epoxy resin composition.
Embodiment 8
Except using microcapsule-type potentiality solidifying agent 2, replace outside the microcapsule-type potentiality solidifying agent 1 and embodiment 7 same, obtain an one-pack-type epoxy resin composition.
1-4. the evaluating characteristics of microcapsule-type potentiality solidifying agent
Use following method, to the curing characteristics and the storage stability of the one-pack-type epoxy resin composition of embodiment 1～8, and the median size of amine affixture particle 1,2 is estimated.The results are summarized in table 1.
Curing characteristics
For an one-pack-type epoxy resin composition, the DSC7 differential calorimeter that uses Perkin-Elmer society to make is 10 ℃/min at heat-up rate, and measuring temperature range is 30 ℃～300 ℃, and nitrogen atmosphere is measured its effect characteristic down.If the temperature of the maximal point at the curing heating peak that generates then is judged to be " AA ", if be more than 115 ℃ and less than 120 ℃ less than 115 ℃, then be judged to be " A ",, then be judged to be " B " if be more than 120 ℃ and less than 130 ℃, if be more than 130 ℃, then be judged to be " C ".The temperature of the maximal point at the curing heating peak that generates is low more, represents that then resin combination has excellent curability at low temperatures.
Storage stability
In an one-pack-type epoxy resin composition, add the bisphenol A type epoxy resin (epoxy equivalent (weight) is 173g/eq, and hydrolyzable chloride content is 0.01 weight %) of identical weight, in 40 ℃ thermostatic bath, preserve.Use E type viscometer, the viscosity of an one-pack-type epoxy resin composition under 25 ℃ after mensuration initial stage and 30 days.By the viscosity increment rate after initial stage to 30 day, judge storage stability.Viscosimetric analysis, the cone of use 3 ° (angles) is when viscosity is 3～40Pas, rotation number with 10rpm is measured, and when viscosity is 40～200Pas, measures with the rotation number of 2.5rpm, when viscosity is 200～1000Pas, measure with the rotation number of 0.5rpm.If the viscosity increment rate after 30 days is below 25%, then to be judged to be " AA ", if be below 50%, then to be judged to be " A ",, then be judged to be " B " if be less than 100%, more than 100%, then be judged to be " C " if be.
Median size
The median size of amine affixture particle, laser diffraction formula particle size distribution device (the Master sizer 2000: dry type determination unit Scirocco2000), measure 3 times that uses Malvern society to make.And the mean value of general's 50% particle diameter (median particle diameter) at this moment is as median size.
Below, preparation is used for the microcapsule-type potentiality solidifying agent and an one-pack-type epoxy resin composition of comparative example.
Synthesizing of microcapsule-type potentiality solidifying agent 5
In detachable there-necked flask with cooling tube, thermopair, whipping appts, add 45.0g amine affixture particle 1 and 171.0g hexanaphthene, be heated to 40 ℃ after, stir time of 10 minutes.Then, add 3.0g 4,4 '-diphenylmethanediisocyanate heated 2 hours down at 40 ℃.Then, be warming up to 50 ℃, reacted 6 hours.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ hexanaphthene washing and recycling.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains microcapsule-type potentiality solidifying agent 5.
Comparative example 1
Cooperate 33g microcapsule-type potentiality solidifying agent 5 and 67g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and hydrolyzable chloride content is 0.007 weight %), obtain an one-pack-type epoxy resin composition.
Comparative example 2
In detachable there-necked flask with cooling tube, thermopair, whipping appts, (epoxy equivalent (weight) is 173g/eq to add 45g amine affixture particle 1 and 55g bisphenol A type epoxy resin, hydrolyzable chloride content is 0.01 weight %), be heated to 40 ℃ after, add 0.5g water.Stir after 10 minutes, add 4.0g 4,4 '-diphenylmethanediisocyanate heated 2 hours down at 40 ℃.Then, be warming up to 50 ℃, heated 6 hours, the result has carried out curing reaction in flask, can't obtain microcapsule-type potentiality solidifying agent.
Comparative example 3
In detachable there-necked flask with cooling tube, thermopair, whipping appts, (epoxy equivalent (weight) is 173g/eq to add 33g amine affixture particle 1 and 67g bisphenol A type epoxy resin, hydrolyzable chloride content is 0.01 weight %), be heated to 40 ℃ after, add 0.5g water.Stir after 10 minutes, add 4.0g 4,4 '-diphenylmethanediisocyanate heated 2 hours down at 40 ℃.Then, be warming up to 50 ℃, heated 6 hours, obtain microcapsule-type potentiality solidifying agent.
Use and above-mentioned identical method, estimate the curing characteristics and the storage stability of an one-pack-type epoxy resin composition of comparative example 1,3, and microcapsule-type potentiality solidifying agent 5.
Characteristic deviation between different batches relatively
For the composition epoxy resin of embodiment 1,3 and comparative example 1, from the modulation that is synthesized to resin combination of microcapsule-type potentiality solidifying agent, repeat 5 identical experiments, the deviation of research initial stage viscosity.The one-pack-type epoxy resin composition of embodiment 1, the maximum value of its initial stage viscosity is 1.3 divided by the value of minimum value gained, and is that 1 o'clock standard deviation is 0.012 with the minimal viscosity value, deviation is less, and is good.The one-pack-type epoxy resin composition of embodiment 3, the maximum value of its initial stage viscosity is 1.2 divided by the value of minimum value gained, and is that 1 o'clock standard deviation is 0.007 with the minimal viscosity value, deviation is less, and is good.On the other hand, an one-pack-type epoxy resin composition of comparative example 3, the maximum value of its initial stage viscosity is 3.6 divided by the value of minimum value gained, and is that 1 o'clock standard deviation is 0.78 with the minimal viscosity value, deviation is bigger.
Above evaluation result gathers and is shown in table 1.
[table 1]
BisF: bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and water-disintegrable cl content is 0.007wt%)
BisA: bisphenol A type epoxy resin (epoxy equivalent (weight) is 173g/eq, and water-disintegrable cl content is 0.01wt%)
Res: resorcinol diglycidyl ether (epoxy equivalent (weight) is 117g/eq, and water-disintegrable cl content is 0.7wt%)
MDI:4,4 '-diphenylmethanediisocyanate
TDI: tolylene diisocyanate
EG: ethylene glycol
As can be known clear and definite by result shown in the table 1, the microcapsule-type potentiality solidifying agent of the application of the invention, an one-pack-type epoxy resin composition that can obtain having the abundant low-temperature curing characteristic and the storage stability of excellence.
Embodiment 9
Cooperate 30g microcapsule-type potentiality solidifying agent 1, (epoxy equivalent (weight) is 173g/eq to the 50g bisphenol A type epoxy resin, hydrolyzable chloride content is 0.01 weight %) and the 20g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, hydrolyzable chloride content is 0.007 weight %), obtain the one-pack-type epoxy resin composition of embodiment 9.
Embodiment 10,11
Cooperate 30g microcapsule-type potentiality solidifying agent 3 or 6, (epoxy equivalent (weight) is 160g/eq to the 50g bisphenol f type epoxy resin, hydrolyzable chloride content is 0.007 weight %) and the 20g bisphenol A type epoxy resin (epoxy equivalent (weight) is 173g/eq, hydrolyzable chloride content is 0.01 weight %), obtain the one-pack-type epoxy resin composition of embodiment 10,11.
Comparative example 4
In detachable there-necked flask with cooling tube, thermopair, whipping appts, add 30g amine affixture particle 1, (epoxy equivalent (weight) is 173g/eq to the 50g bisphenol A type epoxy resin, hydrolyzable chloride content is 0.01 weight %) and the 20g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, hydrolyzable chloride content is 0.007 weight %), after being heated to 40 ℃, add 0.5g water.Stir after 10 minutes, add 3.0g4,4 '-diphenylmethanediisocyanate heated 2 hours down at 40 ℃.Then, be warming up to 50 ℃, heated 6 hours, obtain an one-pack-type epoxy resin composition.
Comparative example 5
In detachable there-necked flask with cooling tube, thermopair, whipping appts, add 30g amine affixture particle 1, (epoxy equivalent (weight) is 160g/eq to the 50g bisphenol f type epoxy resin, hydrolyzable chloride content is 0.007 weight %) and the 20g bisphenol A type epoxy resin (epoxy equivalent (weight) is 173g/eq, hydrolyzable chloride content is 0.01 weight %), after being heated to 40 ℃, add 0.5g water.Stir after 10 minutes, (Japanese polyurethane society makes, trade(brand)name: Mi Lveleite MR-200), heated 2 hours down at 40 ℃ to add the 3.0g polymeric MDI.Then, be warming up to 50 ℃, heated 6 hours, obtain an one-pack-type epoxy resin composition.
[table 2]
BisF: bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and water-disintegrable cl content is 0.007wt%)
BisA: bisphenol A type epoxy resin (epoxy equivalent (weight) is 173g/eq, and water-disintegrable cl content is 0.01wt%)
PMDI: (Japanese polyurethane society makes polymeric MDI, trade(brand)name: Mi Lveleite MR-200)
MDI:4,4 '-diphenylmethanediisocyanate
As can be known clear and definite by result shown in the table 2, the microcapsule-type potentiality solidifying agent of the application of the invention, not only can obtain having an one-pack-type epoxy resin composition of the abundant low-temperature curing characteristic and the storage stability of excellence, and compare with the same Resins, epoxy of forming, realized promptly having obtained higher flowability than the lower viscosity of amine affixture particle.
(research 2)
2-1. amine affixture particle is synthetic
Amine affixture particle 3
In having the detachable there-necked flask of 3000ml of cooling tube, isobaric dropping funnel, whipping appts, the glyoxal ethyline that in the solution that mixes 1-butanols and toluene gained with 1/1 (wt/wt) of 824.2g, adds 336.4g, in oil bath, be heated to 80 ℃ while stirring, make the glyoxal ethyline fusion.Then, use isobaric dropping funnel, splashed into following solution in 90 minutes, described solution is that the bisphenol A type epoxy resin of 945.8g (epoxy equivalent (weight) is 173g/eq, and hydrolyzable chloride content is 0.01 weight %) is dissolved in the solution in 300g 1-butanols and toluene 1/1 (wt/wt) solution.After splashing into end, heated 5 hours down at 80 ℃.Then, be warming up to 180 ℃, and to be decompressed to resulting pressure in will installing be below the 10mmHg.Heat up in a steamer and desolvate.After pressure reaches below the 10mmHg, further, heat up in a steamer and desolvate by under reduced pressure heating 2 hours, obtain the thick liquid of chocolate.This thick liquid is cooled to room temperature, obtains the solid state amine affixture of chocolate.Use jet mill to pulverize this amine affixture, obtaining median size is the amine affixture particle 3 of 2.50 μ m.
Amine affixture particle 4
Except bisphenol A type epoxy resin being changed into outside the 874g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and hydrolyzable chloride content is 0.007 weight %), use the method identical with amine affixture 1, obtaining median size is the amine affixture particle 4 of 3.14 μ m.
2-2. microcapsule-type potentiality solidifying agent is synthetic
Microcapsule-type potentiality solidifying agent 7
In detachable there-necked flask, add 45.0g amine affixture particle 1 and 171.0g hexanaphthene, and after being heated to 40 ℃, add 1.1g water with cooling tube, thermopair, whipping appts.Stir after 10 minutes, add 6.0g 4,4 '-diphenylmethanediisocyanate makes it react 2 hours down at 40 ℃.Then, be warming up to 50 ℃, reacted 6 hours.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ hexanaphthene washing and recycling.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains microcapsule-type potentiality solidifying agent 7.The ratio of the capsule in the microcapsule-type potentiality solidifying agent 7 of gained is 14 quality %.
Microcapsule-type potentiality solidifying agent 8
In the detachable there-necked flask of the 500mL with cooling tube, thermopair, whipping appts, add 45.0g amine affixture particle 1 and 171.0g hexanaphthene, and after being heated to 40 ℃, add 1.1g water.Then, add 3.0g 4,4 '-diphenylmethanediisocyanate makes it react 2 hours down at 40 ℃.Further be warming up to 50 ℃, reacted 6 hours.After reaction finishes, filter dispersion liquid, and the powder that reclaims with toluene wash.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains pulverous microcapsule-type potentiality solidifying agent 8.The ratio of the capsule in the microcapsule-type potentiality solidifying agent 8 of gained is 9 quality %.
Microcapsule-type potentiality solidifying agent 9
In detachable there-necked flask, add 45.0g amine affixture particle 2 and 171.0g hexanaphthene, and after being heated to 40 ℃, add 1.1g water with cooling tube, thermopair, whipping appts.Stir after 10 minutes, add 6.0g 4,4 '-diphenylmethanediisocyanate makes it react 2 hours down at 40 ℃.Then, be warming up to 50 ℃, reacted 6 hours.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ hexanaphthene washing and recycling.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains pulverous microcapsule-type potentiality solidifying agent 9.The ratio of the capsule in the microcapsule-type potentiality solidifying agent 9 of gained is 15 quality %.
Microcapsule-type potentiality solidifying agent 10 (capsuleization again of microcapsule-type potentiality solidifying agent 7)
In the detachable there-necked flask of the 500mL with cooling tube, thermopair, whipping appts, add 146.3g toluene and 3.7g 4,4 '-diphenylmethanediisocyanate, and in oil bath, be heated to 50 ℃.Then, add 15.0g microcapsule-type potentiality solidifying agent 7, reacted 3 hours down at 50 ℃.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ toluene wash recovery.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains pulverous microcapsule-type potentiality solidifying agent 10.The ratio of the capsule in the microcapsule-type potentiality solidifying agent 10 of gained is 45 quality %.
Microcapsule-type potentiality solidifying agent 11 (capsuleization again of microcapsule-type potentiality solidifying agent 7)
In the detachable there-necked flask of the 500mL with cooling tube, thermopair, whipping appts, add 146.3g toluene and 1.8g 4,4 '-diphenylmethanediisocyanate, and in oil bath, be heated to 50 ℃.Then, add 15.0g microcapsule-type potentiality solidifying agent 7, reacted 3 hours down at 50 ℃.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ toluene wash recovery.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains pulverous microcapsule-type potentiality solidifying agent 11.The ratio of the capsule in the microcapsule-type potentiality solidifying agent 11 of gained is 28 quality %.
2-3. the modulation of an one-pack-type epoxy resin composition
Embodiment 12～16
The microcapsule-type potentiality solidifying agent 7～11 and the 67g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and hydrolyzable chloride content is 0.007 weight %) that cooperate 33g respectively obtain the one-pack-type epoxy resin composition of embodiment 12～16.
Embodiment 17
Cooperate 33g microcapsule-type potentiality solidifying agent 10 and 67g bisphenol A type epoxy resin (epoxy equivalent (weight) is 173g/eq, and hydrolyzable chloride content is 0.01 quality %), obtain the one-pack-type epoxy resin composition of embodiment 17.
Embodiment 18
Cooperate 33g microcapsule-type potentiality solidifying agent 10 and 67g naphthalene type Resins, epoxy (epoxy equivalent (weight) is 142g/eq, and hydrolyzable chloride content is 0.017 quality %), obtain the one-pack-type epoxy resin composition of embodiment 18.
Embodiment 19
Cooperate 35g microcapsule-type potentiality solidifying agent 10, (epoxy equivalent (weight) is 160g/eq to the 25g bisphenol f type epoxy resin, hydrolyzable chloride content is 0.007 quality %) and the 40g resorcinol diglycidyl ether (epoxy equivalent (weight) is 117g/eq, hydrolyzable chloride content is 0.7 quality %), obtain the one-pack-type epoxy resin composition of embodiment 19.
2-4. be used for the microcapsule-type potentiality solidifying agent and an one-pack-type epoxy resin composition of comparison
Synthesizing of microcapsule-type potentiality solidifying agent 12
In detachable there-necked flask, add 45.0g amine affixture particle 1 and 171.0g hexanaphthene, and after being heated to 40 ℃, stirred 10 minutes with cooling tube, thermopair, whipping appts.Then, add 1.0g 4,4 '-diphenylmethanediisocyanate reacted 2 hours down at 40 ℃.Then, be warming up to 50 ℃, reacted 6 hours.After reaction finishes, filter dispersion liquid, and with the powder that is heated to 50 ℃ hexanaphthene washing and recycling.By under the pressure below the 10mmHg, drying under reduced pressure 24 hours removes from the powder of gained and desolvates, and obtains microcapsule-type potentiality solidifying agent 12.The ratio of the capsule in the microcapsule-type potentiality solidifying agent 12 of gained is 3 quality %.
Comparative example 6
Cooperate 33g microcapsule-type potentiality solidifying agent 12 and 67g bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and hydrolyzable chloride content is 0.007 quality %), obtain an one-pack-type epoxy resin composition of comparative example 6.
Comparative example 7
In detachable there-necked flask with cooling tube, thermopair, whipping appts, (epoxy equivalent (weight) is 173g/eq to add 45g amine affixture particle 1 and 55g bisphenol A type epoxy resin, hydrolyzable chloride content is 0.01 weight %), be heated to 40 ℃ after, add 0.5g water.Stir after 10 minutes, add 4.0g 4,4 '-diphenylmethanediisocyanate heated 2 hours down at 40 ℃.Then, be warming up to 50 ℃, heated 6 hours, the result has carried out curing reaction in the flask, can't obtain an one-pack-type epoxy resin composition.
Comparative example 8
In detachable there-necked flask with cooling tube, thermopair, whipping appts, (epoxy equivalent (weight) is 160g/eq to add 45g amine affixture particle 1 and 55g bisphenol f type epoxy resin, hydrolyzable chloride content is 0.007 weight %), the result, carry out curing reaction in the flask, can't obtain an one-pack-type epoxy resin composition.
2-5. the evaluating characteristics of microcapsule-type potentiality solidifying agent
Use following method, to the curing characteristics and the storage stability of an one-pack-type epoxy resin composition of embodiment and comparative example, and the median size of amine affixture particle 3,4 is estimated.The result gathers and is shown in table 3.
Curing characteristics
For an one-pack-type epoxy resin composition, the DSC7 differential calorimeter that uses Perkin-Elmer society to make is 10 ℃/min at heat-up rate, and measuring temperature range is 30 ℃～300 ℃, and nitrogen atmosphere is measured its curing characteristics down.If the temperature of the maximal point at the curing heating peak that generates then is judged to be " AA ", if be more than 110 ℃ and less than 125 ℃ less than 110 ℃, then be judged to be " A ",, then be judged to be " B " if be more than 125 ℃ and less than 135 ℃, if be more than 135 ℃, then be judged to be " C ".
Storage stability
Use and study 1 o'clock identical condition determination and benchmark, measure the storage stability of composition epoxy resin and the median size of amine affixture particle.
The ratio of capsule
By at room temperature the synthetic dispersion liquid of methyl alcohol institute of amount stirred 6 hours for adding fully, make the methyl alcohol that is partially dissolved in that comes from amine affixture particle in the microcapsule-type potentiality solidifying agent in microcapsule-type potentiality solidifying agent.Filter dispersion liquid, and under the temperature below 50 ℃ the dry filter thing, thereby remove methyl alcohol fully.The weight of the dried filtrate of weighing.And with the weight of filtrate with respect to the ratio of microcapsule-type hardener for epoxy resin gross weight ratio as capsule.
Solvent resistance
Use toluene/ethyl acetate=1/1 (wt/wt) as solvent, the mixture of one one-pack-type epoxy resin composition/solvent=15g/3.5g is remained in 40 ℃ the water-bath, and the viscosity of observing mixture this moment changes.If the mobile time that becomes nothing is 0～3 hour, then be judged to be " C ", if be 3～6 hours, then be judged to be " B ", if be 6～10 hours, then be judged to be " A ", if be more than 10 hours, then be judged to be " AA ".
2-6. result
The evaluation result of embodiment and comparative example gathers and is shown in following table 3.In the table, the numerical value in the bracket is the proportioning (weight part) of an one-pack-type epoxy resin composition.In the table shortenings the contents are as follows described.
BisA: bisphenol A type epoxy resin (epoxy equivalent (weight) is 173g/eq, and hydrolyzable chloride content is 0.01 quality %)
BisF: bisphenol f type epoxy resin (epoxy equivalent (weight) is 160g/eq, and hydrolyzable chloride content is 0.007 quality %)
Nap: naphthalene type Resins, epoxy (epoxy equivalent (weight) is 142g/eq, and hydrolyzable chloride content is 0.017 quality %)
Res: resorcinol diglycidyl ether (epoxy equivalent (weight) is 117g/eq, and hydrolyzable chloride content is 0.7 quality %)
[table 3]
Also can confirm by above-mentioned experimental result, according to the present invention, the used for epoxy resin Powdered microcapsule-type potentiality solidifying agent and the manufacture method thereof that can obtain curability at low temperatures and storage stability and deposit, and an one-pack-type epoxy resin composition.
Claims (14)
1. used for epoxy resin microcapsule-type potentiality solidifying agent, the capsule that it has nuclear and coats this nuclear, described nuclear comprises the amine affixture, described capsule comprises isocyanic ester and the resultant of reaction with compound bearing active hydrogen and/or water, and at least a portion of this resultant of reaction is bonded to described nuclear by the reaction with described amine affixture.
2. used for epoxy resin microcapsule-type potentiality solidifying agent as claimed in claim 1, wherein, it is 50～100% described amine affixture by quality ratio that described nuclear comprises.
3. microcapsule-type potentiality solidifying agent as claimed in claim 1, it is Powdered.
4. microcapsule-type potentiality solidifying agent as claimed in claim 1, wherein, the ratio of described capsule is a benchmark with the total mass of this microcapsule-type potentiality solidifying agent, is 5～80 quality %.
5. microcapsule-type potentiality solidifying agent as claimed in claim 1, wherein, the ratio of described capsule is a benchmark with the total mass of this microcapsule-type potentiality solidifying agent, is 40～80 quality %.
6. microcapsule-type potentiality solidifying agent as claimed in claim 1, wherein, the ratio of described capsule is a benchmark with the total mass of this microcapsule-type potentiality solidifying agent, is 15～40 quality %.
7. microcapsule-type potentiality solidifying agent as claimed in claim 1, wherein, the ratio of described capsule is a benchmark with the total mass of this microcapsule-type potentiality solidifying agent, is 5～15 quality %.
8. the manufacture method of a used for epoxy resin microcapsule-type potentiality solidifying agent, it comprises makes amine affixture, the isocyanic ester that nuclear comprises and have compound bearing active hydrogen and/or water reacts in dispersion medium, forms the operation of the capsule that coats described nuclear thus.
9. manufacture method as claimed in claim 8, it further comprises from post reaction mixture, takes out the operation of the pulverous microcapsule-type potentiality solidifying agent with nuclear and capsule.
10. the used for epoxy resin microcapsule-type potentiality solidifying agent that obtains by the described manufacture method of claim 8.
11. an one-pack-type epoxy resin composition, it contains each described used for epoxy resin microcapsule-type potentiality solidifying agent and Resins, epoxy in claim 1～7 and 10.
12. an one-pack-type epoxy resin composition as claimed in claim 11, wherein, described used for epoxy resin microcapsule-type potentiality solidifying agent has carried out heat treated in described Resins, epoxy.
13. an one-pack-type epoxy resin composition as claimed in claim 11 wherein, with respect to total amount 100 mass parts of described Resins, epoxy and described microcapsule-type potentiality solidifying agent, contains the described microcapsule-type potentiality of 5～70 mass parts solidifying agent.
14. make the described one-pack-type epoxy resin composition of claim 11 solidify formed cured article by heating.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-243851 | 2007-09-20 | ||
| JP2007-243852 | 2007-09-20 | ||
| JP2007243852 | 2007-09-20 | ||
| JP2007243851 | 2007-09-20 | ||
| JP2008043346 | 2008-02-25 | ||
| JP2008-043346 | 2008-02-25 | ||
| JP2008166246 | 2008-06-25 | ||
| JP2008-166246 | 2008-06-25 | ||
| PCT/JP2008/066774 WO2009038097A1 (en) | 2007-09-20 | 2008-09-17 | Microcapsule-type latent curing agent for epoxy resin and process for production thereof, and one-pack-type epoxy resin composition and cured product thereof |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2012104288004A Division CN102936331A (en) | 2007-09-20 | 2008-09-17 | Microcapsule-type latent curing agent for epoxy resin and process for production thereof |
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| CN101802050A true CN101802050A (en) | 2010-08-11 |
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| CN200880107917A Pending CN101802050A (en) | 2007-09-20 | 2008-09-17 | Microcapsule-type latent curing agent for epoxy resin and process for production thereof, and one-pack-type epoxy resin composition and cured product thereof |
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| JP (1) | JP5158088B2 (en) |
| KR (2) | KR101243511B1 (en) |
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| CN116323837A (en) * | 2020-09-30 | 2023-06-23 | 旭化成株式会社 | Polyurethane curing agent and its application |
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| KR101086701B1 (en) * | 2009-06-10 | 2011-11-25 | 한국과학기술연구원 | Latent curing agent composite particles with improved storage stability using physicochemical bonding system and preparation method |
| KR102270461B1 (en) * | 2016-03-10 | 2021-06-29 | 한국전자기술연구원 | Adhesive composition and preparing method thereof |
| KR101870777B1 (en) * | 2017-03-28 | 2018-06-26 | 한국신발피혁연구원 | Manufacturing method of microcapsule type latent curing agent and microcapsule type latent curing agent using the same |
| KR102095115B1 (en) * | 2018-07-27 | 2020-03-30 | 한국전력공사 | Self-healing silicon insulator and manufacturing method for thereof |
| CN111087576A (en) * | 2019-12-31 | 2020-05-01 | 芜湖天道绿色新材料有限公司 | Preparation and application of degradable microcapsule curing agent |
| CN111171285B (en) * | 2020-02-15 | 2022-04-26 | 常州大学 | A kind of epoxy resin curing agent microcapsule with polyurethane as shell material and preparation method thereof |
| CN111518500B (en) * | 2020-04-22 | 2023-04-11 | 湖北回天新材料股份有限公司 | Solvent type single-component epoxy microcapsule precoated thread locking glue and preparation method thereof |
| CN111389317B (en) * | 2020-04-28 | 2022-04-12 | 西北工业大学 | Preparation method of imidazole microcapsules based on mercapto-isocyanate click reaction and oil-in-oil interfacial polymerization |
| WO2023286499A1 (en) * | 2021-07-12 | 2023-01-19 | 旭化成株式会社 | Epoxy resin composition, film, film production method, and cured product |
| CN114230767B (en) * | 2021-12-13 | 2024-03-19 | 江苏钛得新材料技术有限公司 | Imidazole derivative microcapsule type latent curing agent for adhesive and preparation method thereof |
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| JP3611439B2 (en) * | 1998-01-12 | 2005-01-19 | 株式会社日立製作所 | Microcapsule-type phosphorus curing accelerator and epoxy resin composition for semiconductor encapsulation using the same |
| JP4567377B2 (en) * | 2004-06-04 | 2010-10-20 | 旭化成イーマテリアルズ株式会社 | Latent curing agent and composition |
| WO2007037378A1 (en) * | 2005-09-29 | 2007-04-05 | Asahi Kasei Chemicals Corporation | High-stability microencapsulated hardener for epoxy resin and epoxy resin composition |
| JP4877717B2 (en) * | 2005-09-29 | 2012-02-15 | 旭化成イーマテリアルズ株式会社 | Curing agent for slow-reactive epoxy resin and epoxy resin composition |
| JP2007091899A (en) * | 2005-09-29 | 2007-04-12 | Asahi Kasei Chemicals Corp | Highly stable curing agent for epoxy resin and epoxy resin composition |
| JP4877716B2 (en) * | 2005-09-29 | 2012-02-15 | 旭化成イーマテリアルズ株式会社 | Curing agent for fast-curing epoxy resin and epoxy resin composition |
| JP4911981B2 (en) * | 2006-02-03 | 2012-04-04 | 旭化成イーマテリアルズ株式会社 | Curing agent for highly water-containing solvent-containing epoxy resin and epoxy resin composition |
| KR100976303B1 (en) * | 2006-02-03 | 2010-08-16 | 아사히 가세이 케미칼즈 가부시키가이샤 | Hardener for microcapsule type epoxy resin, Hardener composition for masterbatch type epoxy resin, One-component epoxy resin composition, and processed product |
| JP2007204669A (en) * | 2006-02-03 | 2007-08-16 | Asahi Kasei Chemicals Corp | Specific small particle size particle size distribution epoxy resin curing agent and epoxy resin composition |
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| CN116323837A (en) * | 2020-09-30 | 2023-06-23 | 旭化成株式会社 | Polyurethane curing agent and its application |
| CN116323837B (en) * | 2020-09-30 | 2024-10-25 | 旭化成株式会社 | Polyurethane curing agent and application thereof |
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| Publication number | Publication date |
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| JPWO2009038097A1 (en) | 2011-01-06 |
| KR20120024963A (en) | 2012-03-14 |
| CN102936331A (en) | 2013-02-20 |
| JP5158088B2 (en) | 2013-03-06 |
| WO2009038097A1 (en) | 2009-03-26 |
| TW201008971A (en) | 2010-03-01 |
| KR101243511B1 (en) | 2013-03-20 |
| KR20100072030A (en) | 2010-06-29 |
| TW201244814A (en) | 2012-11-16 |
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Effective date of abandoning: 20100811 |
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| C20 | Patent right or utility model deemed to be abandoned or is abandoned |