WO2012035865A1 - 潜在性硬化剤の製造方法 - Google Patents
潜在性硬化剤の製造方法 Download PDFInfo
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- WO2012035865A1 WO2012035865A1 PCT/JP2011/065963 JP2011065963W WO2012035865A1 WO 2012035865 A1 WO2012035865 A1 WO 2012035865A1 JP 2011065963 W JP2011065963 W JP 2011065963W WO 2012035865 A1 WO2012035865 A1 WO 2012035865A1
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- WIPO (PCT)
- Prior art keywords
- resin particles
- porous resin
- imidazole compound
- curing agent
- latent curing
- Prior art date
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- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
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Definitions
- the present invention relates to a method for producing a latent curing agent capable of initiating curing of a thermosetting resin composition mainly composed of an epoxy resin or the like at a relatively low temperature.
- This latent curing agent is an oil-in-water emulsion by emulsifying an oil phase in which a polyfunctional isocyanate compound is dissolved in ethyl acetate into an aqueous phase in which a surfactant and a polyvinyl alcohol as a dispersant are dissolved in water.
- the product is prepared and the emulsion is heated to interfacially polymerize the polyfunctional isocyanate compound in the oil phase to form porous resin particles.
- the porous resin particles are recovered and dried, and then imidazole is added to ethanol. It is manufactured by immersing in an imidazole compound solution in which the compound is dissolved, allowing the imidazole compound solution to permeate the porous resin particles, and collecting, washing, and drying the porous resin particles infiltrated with the imidazole compound solution.
- the latent hardening agent which patent document 1 has proposed has the comparatively intended characteristic regarding latency and low-temperature fast-curing property, the design freedom of a thermosetting epoxy resin composition is obtained. In order to improve, it is required to realize the intended curing characteristics even when the latent curing agent is blended in a smaller amount. In other words, the latent curing agent can be produced while increasing the penetration amount of the imidazole compound solution into the porous resin particles without sacrificing the latency and the low-temperature rapid curing property. It has been demanded.
- the object of the present invention is to solve the above-mentioned problems of the prior art, and to reduce the penetration amount of the imidazole solution into the porous resin particles without sacrificing the latency and the low-temperature rapid curability. It is to produce a latent curing agent so that it can be increased above.
- the inventor of the present invention greatly affects the amount of the imidazole solution penetrating into the porous resin particles due to the dispersant added to the water phase used when emulsifying the oil phase and the water phase containing the polyfunctional isocyanate compound.
- water-soluble polypeptides such as gelatin having amino groups that are reactive with isocyanate groups are used as dispersants, and further, proteolytic enzymes after interfacial polymerization
- the present invention was completed by finding that the above-mentioned object can be achieved by enzymatic treatment.
- the present invention is a method for producing a latent curing agent in which an imidazole compound is held on porous resin particles obtained by interfacial polymerization of a polyfunctional isocyanate compound, and includes the following steps (A) to (E): : Process (A) A step of obtaining an oil-in-water emulsion by emulsifying an oil phase obtained by dissolving a polyfunctional isocyanate compound in an organic solvent into an aqueous phase obtained by dissolving a water-soluble polypeptide and a surfactant in water.
- a production method including a step of obtaining a latent curing agent.
- the present invention also includes a latent curing agent obtained by the above-described production method and a thermosetting resin, and the thermosetting resin composition, the thermosetting resin composition, An anisotropic conductive adhesive film formed by dispersing conductive particles for anisotropic conductive connection into a film and an adhesive film for solar cells formed by forming the thermosetting resin composition into a film are provided.
- a water-soluble polypeptide such as gelatin is used as a dispersant in an aqueous phase during interfacial polymerization.
- a water-soluble polypeptide has an amino group or a carboxyl group that reacts with an isocyanate group. Therefore, a polypeptide structure derived from a water-soluble polypeptide is introduced on or near the surface of the porous resin particles that are intermediate products of the production method of the present invention.
- porous resin particles into which such a polypeptide structure is introduced are subjected to proteolytic enzyme treatment.
- the polypeptide structure is decomposed into amino acids and oligopeptides, so that the imidazole solution of porous resin particles is compared to the case of conventional porous resin particles obtained by interfacial polymerization using polyvinyl alcohol as a dispersant.
- Improves permeability Therefore, when the latent curing agent obtained by the production method of the present invention is blended in a thermosetting resin composition, it becomes possible to achieve the same curing characteristics with a smaller blending amount than conventional latent curing agents. Moreover, such a thermosetting resin composition exhibits good low-temperature fast curing properties.
- FIG. 1A is a particle size distribution diagram of porous resin particles of Example 1.
- FIG. 1B is an electron micrograph (5000 magnifications) of the porous resin particles of Example 1.
- FIG. 1C is an electron micrograph (20,000 times) of the porous resin particles of Example 1.
- FIG. 2 is an electron micrograph (5000 magnifications) of porous resin particles of Reference Example 1.
- 1 is a DSC measurement diagram of thermosetting fat compositions of Examples 1 to 3.
- FIG. It is a DSC measurement figure of the thermosetting resin composition of Example 1 and Examples 4 and 5.
- 1 is a DSC measurement diagram of thermosetting resin compositions of Example 1 and Examples 6 to 8.
- FIG. 3 is a TG-DTA measurement diagram of the latent curing agent of Comparative Example 1, the porous resin particles of Example 1, and the latent curing agent of Example 6.
- FIG. 10 is a DSC measurement diagram of test results of Example 9.
- FIG. 10 is a DSC measurement diagram of test results of Example 9.
- FIG. 10 is
- the present invention is a method for producing a latent curing agent in which an imidazole compound is held on porous resin particles obtained by interfacial polymerization of a polyfunctional isocyanate compound, and includes the following steps (A) to (E): .
- steps (A) to (E): include the following steps (A) to (E): .
- step (A) an oil phase obtained by dissolving a polyfunctional isocyanate compound in an organic solvent is emulsified in an aqueous phase obtained by dissolving a water-soluble polypeptide and a surfactant in water to form oil-in-water droplets. This is a step of obtaining a mold emulsion.
- step (A) first, a polyfunctional isocyanate compound is dissolved in an organic solvent to prepare a solution that becomes an oil phase in interfacial polymerization.
- the organic solvent is preferably volatile. The reason is as follows. That is, when a high boiling point solvent having a boiling point exceeding 300 ° C. as used in a normal interfacial polymerization method is used, the organic solvent does not volatilize during the interfacial polymerization, so the contact probability between isocyanate and water does not increase. This is because the degree of progress of interfacial polymerization between them becomes insufficient.
- thermosetting resin composition a thermosetting resin composition
- the high boiling point solvent adversely affects the physical properties of the cured product of the thermosetting resin composition. For this reason, a volatile thing is used as an organic solvent used when preparing an oil phase.
- Such an organic solvent is a good solvent for a polyfunctional isocyanate compound (solubility is preferably 0.1 g / ml (organic solvent) or more) and does not substantially dissolve in water (water solubility). Is 0.5 g / ml (organic solvent) or less) and has a boiling point of 100 ° C. or less under atmospheric pressure.
- Specific examples of such an organic solvent include alcohols, acetate esters, ketones and the like. Among them, ethyl acetate can be preferably used in terms of high polarity, low boiling point, and poor water solubility.
- the amount of the organic solvent used is preferably 1.5 to 5 times, more preferably 1.5 times the amount of the polyfunctional isocyanate compound, because if the amount is too small, the latency will decrease and if it is too large, the thermal response will decrease. -3 mass times. If the amount of the organic solvent is relatively large, hydrolysis of the isocyanate group is suppressed during emulsification, and the reaction between the amino group of the water-soluble polypeptide in the aqueous phase and the isocyanate group of the isocyanate compound in the oil phase. Tend to be competitive, and the shape of the porous resin particles obtained after interfacial polymerization tends to be irregular spherical. On the other hand, when the amount of the organic solvent is relatively reduced, the interfacial polymerizability of the isocyanate compound is improved, and the shape of the porous resin particles obtained after interfacial polymerization tends to be spherical.
- the viscosity of the solution which becomes an oil phase can be lowered by using a relatively large amount of the organic solvent within the range of the amount of the organic solvent used. Lowering the viscosity improves the stirring efficiency, making it possible to make the oil phase droplets in the reaction system finer and more uniform.
- the resulting latent curing agent particle size is about submicron to several microns. It is possible to make the particle size distribution monodisperse while controlling to the size of. From such a viewpoint, it is preferable to set the viscosity of the oil phase solution to 1 to 500 mPa ⁇ s.
- the polyfunctional isocyanate compound When the polyfunctional isocyanate compound is dissolved in the organic solvent, it may be simply mixed and stirred at room temperature under atmospheric pressure, but may be heated as necessary.
- the polyfunctional isocyanate compound used in the present invention is preferably a compound having two or more isocyanate groups, preferably three isocyanate groups in one molecule.
- a TMP adduct of formula (2) obtained by reacting 3 mol of a diisocyanate compound with 1 mol of trimethylolpropane, and a formula (3) obtained by self-condensing 3 mol of a diisocyanate compound.
- An isocyanurate of formula (4) and a biuret of formula (4) obtained by condensing the remaining 1 mol of diisocyanate with diisocyanate urea obtained from 2 mol of 3 mol of diisocyanate compound.
- the substituent R is a portion excluding the isocyanate group of the diisocyanate compound.
- diisocyanate compounds include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, m-xylylene diisocyanate, hexamethylene diisocyanate, hexahydro-m-xylylene diisocyanate, isophorone diisocyanate, methylene diphenyl-4. 4,4'-diisocyanate.
- an aqueous phase in which a surfactant and a water-soluble polypeptide are dissolved in water is prepared.
- the water-soluble polypeptide functions as a dispersant for dispersing porous resin particles described later in the aqueous phase.
- the water-soluble level of the water-soluble polypeptide is a level that dissolves at least 1 g in 100 g of distilled water at 40 ° C.
- water-soluble polypeptides include collagen peptides, gelatin, and casein.
- gelatin is preferable from the viewpoint of average molecular weight, and further, acid-treated gelatin can be preferably used from the viewpoint of enabling control of the particle size of a single micrometer.
- gelatin having a relatively low jelly strength can be preferably used. Specifically, it is preferable to use gelatin exhibiting a jelly strength of 10 to 250 according to JIS K6503-2001. Further, from the viewpoint of emulsion dispersion stability, it is preferable to use gelatin having a weight average molecular weight of 1,000 to 110,000.
- water distilled water and ion-exchanged water can be preferably used. If the content of the water-soluble polypeptide such as gelatin relative to water is too small, the emulsification becomes unstable, and if it is too large, the emulsification dispersibility is lowered. More preferably, it is 0.1 to 10 parts by mass. In addition, since the water-soluble polypeptide such as gelatin is too low with respect to the polyfunctional isocyanate compound used, it becomes low reactivity, and when it is too much, it becomes highly reactive. 1 to 50 parts by mass, more preferably 1 to 30 parts by mass.
- a surfactant is included for emulsification stability.
- alkylbenzene sulfonate can be preferably used from the viewpoint of isocyanate reactivity and non-halogen. If the surfactant content is too small, the emulsion stability decreases, and if it is too large, fine particles are formed and foamed, and therefore it is preferably 0.001 to 10 per 100 parts by mass of distilled water or the like. Part by mass, more preferably 0.001 to 0.1 part by mass.
- step (A) the oil phase in which the polyfunctional isocyanate compound described above is dissolved in an organic solvent is added to an aqueous phase containing a surfactant and gelatin and emulsified to form an oil-in-water emulsion.
- the mixing ratio of the oil phase to the water phase is preferably 5 to 80 parts by mass with respect to 100 parts by mass of the aqueous phase, because if the oil phase is too small, polydispersion occurs, and if it is too much, aggregation occurs due to refinement. is there.
- stirring conditions such that the volume average particle diameter of the oil phase is preferably 0.5 to 100 ⁇ m, more preferably 0.5 to 30 ⁇ m (for example, a stirrer homogenizer; stirring speed 6000 to 25000 rpm, atmospheric pressure) Room temperature, stirring time 1 to 30 minutes).
- Step (B) is a step of forming porous resin particles by interfacial polymerization of the polyfunctional isocyanate compound in the oil phase by heating the oil-in-water emulsion prepared in step (A).
- the interfacial polymerization can be carried out following the step (A). For example, using a known stirrer equipped with a bladed stirrer, at a stirring speed of 10 to 300 rpm, usually at atmospheric pressure and a temperature of 30 to 80 It can be carried out by heating and stirring at a temperature of 2 ° C. for 2 to 12 hours. In addition, a process (A) and a process (B) can also be performed simultaneously.
- Porous resin particles obtained by interfacial polymerization of such a polyfunctional isocyanate compound undergo a hydrolysis of a part of the isocyanate groups during the interfacial polymerization to become amino groups, which react with the amino groups. It is a porous polyurea that forms a urea bond to polymerize.
- the water-soluble polypeptide which is a dispersant is one in which the amino group or carboxyl group reacts with an isocyanate group
- the polypeptide structure part derived from the water-soluble polypeptide is formed on the surface of the porous resin particle by interfacial polymerization. It is introduced in the vicinity.
- the proteolytic enzyme is added to the interfacial polymerization reaction liquid in which the porous resin particles prepared in the step (B) are dispersed at a time or little by little, and the porous resin particles are subjected to the enzymatic decomposition treatment. It is.
- the enzymatic decomposition treatment the polypeptide structure portion introduced on or near the surface of the porous resin particles is enzymatically decomposed, and as a result, the permeability of the imidazole compound solution into the porous resin particles is improved.
- proteolytic enzyme a known proteolytic enzyme can be used, and examples thereof include protease N “Amano G”, Newase F3G, Promeline F (Amano Enzyme Co., Ltd.) and the like. If the amount of the proteolytic enzyme used is too small, the peptide structure will be insufficiently decomposed, and if it is too much, residual foreign matter will be formed. 50 parts by mass, more preferably 1 to 30 parts by mass.
- the enzyme treatment can be performed by adjusting the interfacial polymerization reaction solution charged with the proteolytic enzyme to an enzyme activity temperature range (for example, 30 to 60 ° C.) while stirring.
- the stirring time varies depending on the temperature, the desired degree of decomposition, and the like, but is usually 1 to 12 hours.
- Step (D) is a step of recovering the porous resin particles subjected to the enzymatic decomposition treatment in step (C) from the interfacial polymerization reaction solution.
- the recovered porous resin particles are preferably further dried.
- recovery method It can carry out by a well-known method. Further, after the recovery, it may be washed with an organic solvent such as water or a hydrocarbon solvent.
- the drying treatment can be performed by a known drying method such as natural drying or vacuum drying.
- the porous resin particles after recovery or drying can be crushed using a jet mill or the like for primary particle formation.
- step (E) the porous resin particles obtained in step (D) are mixed with an imidazole compound solution obtained by dissolving an imidazole compound in an organic solvent, and the imidazole compound solution is infiltrated into the porous resin particles.
- the latent curing agent obtained by holding the imidazole compound on the porous resin particles is obtained by collecting, washing, and drying according to the above.
- the imidazole compound a known imidazole compound used as a curing agent such as an epoxy resin can be used.
- 2-methylimidazole (melting point: 137-145 ° C.), 2-undecylimidazole (melting point: 69-74 ° C.), 2-heptadecylimidazole (melting point: 86-91 ° C.), 1,2-dimethylimidazole (melting point: about 36 ° C), 2-ethyl-4-methylimidazole (melting point about 41 ° C), 2-phenylimidazole (melting point 137-147 ° C), 2-phenyl-4-methylimidazole (melting point 174-184 ° C), 1-benzyl- Examples thereof include 2-methylimidazole (melting point: about 50 ° C.) and 1-benzyl-2-phenylimidazole (melting point: about 40 ° C.). These may be used alone or in combination of two or more.
- the imidazole compound contains two imidazole compounds
- the organic solvent for dissolving the imidazole compound as described above is a good solvent for the imidazole compound (the solubility is preferably 0.1 g / ml (organic solvent) or higher), and the boiling point under atmospheric pressure is 100 ° C. or lower. Those are preferred. Specific examples of such an organic solvent include alcohols, acetate esters, ketones and the like. Of these, ethanol is preferred because of its high polarity and low boiling point.
- the amount of the organic solvent used is too small relative to the imidazole compound, the imidazole solution permeability of the porous resin particles will decrease, and if too large, the absolute amount of the imidazole compound that penetrates into the porous resin particles will decrease.
- the amount is preferably 1 to 5 times by mass, more preferably 1 to 3 times by mass.
- the imidazole compound solution preferably further contains a tertiary amine compound used as a curing accelerator for the epoxy compound.
- a tertiary amine compound used as a curing accelerator for the epoxy compound.
- tertiary amine compounds include dimethylethanolamine, dimethylbenzylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene and the like. Can do.
- 2,4,6-tris (dimethylaminomethyl) phenol can be preferably used from the viewpoint of curing acceleration effect.
- the amount of such a tertiary amine compound is too small relative to the imidazole compound, the fast curability is lowered, and if it is too much, the low-temperature curability is lowered. More preferably, it is 0.1 to 0.8 times by mass.
- the imidazole compound solution as described above is mixed with the enzymatic resin-treated porous resin particles obtained in the step (D), thereby allowing the imidazole compound solution to permeate the porous resin particles.
- this infiltration operation is carried out by heating or stirring at room temperature for 24 hours.
- the porous resin particles are recovered from the imidazole compound solution by a conventional method, preferably washed with water, and vacuum dried to obtain a latent curing agent in which the imidazole compound is held on the porous resin particles. Can be acquired. If necessary, the latent curing agent can be crushed by a jet mill or the like.
- the latent curing agent thus obtained is preferably subjected to sublimation removal of the imidazole compound on the surface and in the vicinity thereof by heat treatment in order to improve the thermal stability and latency.
- the heat treatment temperature is 80 to 120 ° C.
- the heat treatment time is usually 0.25 to 1 hour.
- the latent amount can be increased by changing the type and amount of the polyfunctional isocyanate compound, the type and amount of the water-soluble polypeptide, the interfacial polymerization conditions, the proteolytic enzyme treatment conditions, and the like. It is possible to control the curing characteristics of the adhesive curing agent. For example, if the polymerization temperature is lowered, the curing temperature can be lowered, and conversely, if the polymerization temperature is raised, the curing temperature can be raised.
- the latent curing agent thus obtained can be used in the same applications as conventional imidazole-based latent curing agents, and when used in combination with a thermosetting resin, a low-temperature fast-curing thermosetting type A resin composition can be provided.
- the amount is preferably 1 to 70 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the thermosetting resin.
- thermosetting resin a thermosetting epoxy resin, a thermosetting urea resin, a thermosetting melamine resin, a thermosetting phenol resin, or the like can be used.
- a thermosetting epoxy resin can be preferably used in consideration of a good adhesive strength after curing.
- thermosetting epoxy resin may be liquid or solid, and preferably has an epoxy equivalent of usually about 100 to 4000 and having two or more epoxy groups in the molecule.
- a bisphenol A type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, an ester type epoxy compound, an alicyclic epoxy compound, or the like can be preferably used. These compounds include monomers and oligomers.
- thermosetting resin composition of the present invention may contain a filler such as silica and mica, a silane coupling agent, a pigment, an antistatic agent, and the like as necessary.
- thermosetting resin composition of the present invention is produced by uniformly mixing and stirring the latent curing agent of the present invention, the thermosetting resin, and other additives added as necessary according to a conventional method. be able to.
- thermosetting resin composition of the present invention uses the latent curing agent of the present invention, so even if the latent curing agent is blended in a relatively smaller amount than before, It can be cured without impairing the low temperature fast curing property.
- thermosetting resin composition of the present invention can be formed into a film and preferably used as an adhesive film for solar cells. Further, known anisotropic conductive connecting conductive particles can be dispersed in the composition to form a film, which can be preferably used as an anisotropic conductive adhesive film.
- Example 1 Preparation of porous resin particles> A thermometer containing 840 parts by weight of distilled water, 0.05 part by weight of a surfactant (Newlex RT, NOF Corporation) and 8 parts by weight of gelatin (AP100 fine powder, Nitta Gelatin Co., Ltd.) In a 3 liter interfacial polymerization vessel and mixed uniformly. Further, 150 parts by mass of a trimethylolpropane (1 mol) adduct (D-109, Mitsui Chemicals, Inc.) of methylenediphenyl-4,4'-diisocyanate (3 mol) was added to this mixed solution and 450 parts by mass of ethyl acetate.
- a trimethylolpropane (1 mol) adduct D-109, Mitsui Chemicals, Inc.
- the oil phase dissolved in the part is charged and emulsified and mixed for 5 minutes using a homogenizer (T-65D, IKA Japan) at 7200 rpm at room temperature so that the volume-converted average particle size is 10 ⁇ m or less.
- a homogenizer T-65D, IKA Japan
- An oil droplet type emulsion was obtained.
- the emulsion was heated to 80 ° C. while stirring with a bladed stirring rod, and interfacial polymerization was performed by continuing stirring at this temperature for 3 hours to obtain a polymerization reaction liquid in which porous resin particles were dispersed in an aqueous phase. It was.
- the polymerization reaction solution was adjusted to 40 ° C., 0.8 parts by mass of the enzyme (Protease N “Amano G”, Amano Enzyme Co., Ltd.) was added, and the mixture was made porous by stirring at 40 ° C. for 6 hours.
- the enzyme treatment of the resin particles was performed. After the enzyme treatment, the porous resin particles were collected from the polymerization reaction solution by filtration, washed with water, and dried to obtain spherical porous resin particles of Example 1.
- the particle size distribution of the obtained porous resin particles was measured using a particle size distribution measuring device (SD-2000, Sysmex Corporation), and the obtained distribution chart is shown in FIG. 1A. Moreover, an electron micrograph is shown in FIG. 1B (5000 times magnification) and FIG. 1C (20000 times magnification). For reference, an electron micrograph (5000 times magnification) of the porous resin particles of Reference Example 1 prepared in the same manner except that the amount of ethyl acetate used was changed from 450 parts by mass to 200 parts by mass during the preparation of the oil phase is shown in FIG. 1D. Shown in
- FIG. 1A shows that the average particle size (volume conversion) is 2.5 ⁇ m and the maximum particle size is 6.6 ⁇ m.
- the permeability of the imidazole compound solution will decrease due to the spherical shape, and the absence of surface irregularities suppresses the adverse effect on the curing characteristics of the latent curing agent due to the jet mill crushing treatment. Can be expected.
- ⁇ Infiltration treatment of imidazole compound 10 parts by mass of the obtained porous resin particles of Example 1 were dissolved in 60 parts by mass of ethanol and 40 parts by mass of 2-methylimidazole (2MZ-H, Shikoku Chemicals Co., Ltd.) having a melting point of 137 to 145 ° C. The solution was added to 100 parts by mass and stirred at 30 ° C. for 6 hours at 200 rpm. Thereafter, stirring was continued at room temperature for 20 hours. After completion of the stirring, the porous resin particles treated with the imidazole compound were collected by filtration, washed with distilled water, dried in vacuum, and further dissolved by a jet mill (AO-JET MILL, Seisin Co., Ltd.). It was crushed to form primary particles. Thereby, a latent curing agent was obtained.
- 2-methylimidazole 2MZ-H, Shikoku Chemicals Co., Ltd.
- thermosetting resin composition Uniformly blend 20 parts by mass of the resulting latent curing agent into 80 parts by mass of a bisphenol A type liquid epoxy resin (EP828, Mitsubishi Chemical Corporation) using a kneader (Awatori Netaro, Inc. Shinky Co., Ltd.). A thermosetting resin composition was obtained by mixing.
- thermosetting resin composition was subjected to differential thermal scanning calorimetry using a differential thermal scanning calorimeter (DSC) (DSC6200, Seiko Instruments Inc.) (evaluation amount 5 mg, heating rate 10 ° C.). / Min).
- DSC differential thermal scanning calorimeter
- the exothermic start temperature means the curing start temperature
- the exothermic peak temperature means the temperature at which curing is most active
- the total calorific value is the value of the curing reaction. It means the amount of heat generated from the start to completion.
- Example 2 A latent curing agent was prepared in the same manner as in Example 1, except that 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) having a melting point of 41 ° C. was used instead of 2-methylimidazole. Further, a thermosetting resin composition was prepared using the same. About the obtained thermosetting resin composition, differential thermal scanning calorimetry was performed similarly to Example 1, and the obtained result is shown in Table 1 and FIG.
- Example 3 A latent curing agent was prepared in the same manner as in Example 1 except that 2-phenylimidazole (2PZ-PW, Shikoku Kasei Kogyo Co., Ltd.) having a melting point of 137 to 147 ° C. was used instead of 2-methylimidazole. Further, a thermosetting resin composition was prepared using the same. About the obtained thermosetting resin composition, differential thermal scanning calorimetry was performed similarly to Example 1, and the obtained result is shown in Table 1 and FIG.
- thermosetting resin compositions of Examples 1 and 3 using a latent curing agent obtained by infiltrating an imidazole compound having a melting point of 137 ° C. into the porous resin particles are about 110 ° C.
- An exothermic starting temperature and an exothermic peak temperature of a little less than 140 ° C. are shown. Therefore, it can be seen that low temperature rapid curability could be realized while showing the potential.
- thermosetting resin composition of Example 2 using a latent curing agent obtained by impregnating porous resin particles with an imidazole compound having a melting point of 41 ° C. has a heat generation start temperature shifted to about 100 ° C. It can be seen that it has good low-temperature fast curability.
- the same total calorific value as in Examples 1 and 3 was exhibited.
- Example 4 10 parts by mass of 40 parts by mass of 2-methylimidazole was used as a liquid tertiary amine-based curing accelerator, 2,4,6-tris (dimethylaminomethyl) phenol (Lubeak-DMP-30, Nacalai
- a latent curing agent was prepared in the same manner as in Example 1 except that Tex Co., Ltd. was used, and a thermosetting resin composition was prepared using the latent curing agent.
- differential thermal scanning calorimetry was performed similarly to Example 1, and the obtained result is shown in Table 2 and FIG.
- Example 5 Of the 40 parts by mass of 2-methylimidazole, 20 parts by mass of 2,4,6-tris (dimethylaminomethyl) phenol (Lubeak-DMP-30, Nacalai) as a liquid tertiary amine curing accelerator.
- a latent curing agent was prepared in the same manner as in Example 1 except that Tex Co., Ltd. was used, and a thermosetting resin composition was prepared using the latent curing agent.
- differential thermal scanning calorimetry was performed similarly to Example 1, and the obtained result is shown in Table 2 and FIG. For reference, the results of Example 1 are also shown in Table 2 and FIG.
- Example 6 Example 1 except that 10 parts by mass of 40 parts by mass of 2-methylimidazole was used with 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Chemicals Co., Ltd.) having a melting point of 41 ° C.
- a latent curing agent was prepared in the same manner as described above, and a thermosetting resin composition was prepared using the latent curing agent.
- a thermosetting resin composition was prepared using the latent curing agent.
- differential thermal scanning calorimetry was performed similarly to Example 1, and the obtained result is shown in Table 3 and FIG.
- Example 7 Example 1 except that 10 parts by mass of 40 parts by mass of 2-methylimidazole was used with 2-phenylimidazole (2PZ-PW, Shikoku Chemicals Co., Ltd.) having a melting point of 137 to 147 ° C.
- a latent curing agent was prepared in the same manner as described above, and a thermosetting resin composition was prepared using the latent curing agent.
- differential thermal scanning calorimetry was performed similarly to Example 1, and the obtained result is shown in Table 3 and FIG.
- Example 8 10 parts by mass of 40 parts by mass of 2-methylimidazole was used except that 2-phenyl-4-methylimidazole (2P4MZ, Shikoku Kasei Kogyo Co., Ltd.) having a melting point of 174 to 184 ° C. was used.
- a latent curing agent was prepared in the same manner as in Example 1, and a thermosetting resin composition was prepared using the latent curing agent.
- differential thermal scanning calorimetry was performed similarly to Example 1, and the obtained result is shown in Table 3 and FIG. For reference, the results of Example 1 are also shown in Table 3 and FIG.
- Example 1 The latent potential was the same as in Example 1 except that 4 parts by mass of polyvinyl alcohol (PVA-205, Kuraray Co., Ltd.) was used instead of 8 parts by mass of gelatin (AP100 fine powder, Nitta Gelatin Co., Ltd.).
- a curing agent was prepared. About the obtained latent curing agent, the thermogravimetry-differential thermal analyzer (TG-DTA) (TG / DTA6200, Seiko Instruments Inc.) was used to measure the heating weight loss rate (evaluation amount 5 mg, ascending). (Temperature rate 10 ° C./min). The obtained results are shown in Table 4 and FIG.
- the weight loss rate by heating was also measured for the porous resin particles prepared in Example 1 before the imidazole compound infiltration treatment and the latent curing agent prepared in Example 6.
- the obtained results are shown in Table 4 and FIG.
- the weight reduction rate is the ratio of the reduced weight when heated to 260 ° C. (thermal decomposition start temperature) relative to the initial weight
- the encapsulation rate is the porosity of Example 1 before penetration of the imidazole compound solution from the weight reduction rate. This is a value obtained by reducing the weight reduction rate of the resin particles.
- Example 9 (Effect of heat treatment of latent curing agent) Test Example A: A latent curing agent was prepared by repeating Example 4, and a thermosetting resin composition was prepared using the latent curing agent. The resulting thermosetting resin composition was the same as in Example 1. The differential thermal scanning calorimetry was performed, and the obtained results are shown in Table 5 and FIG. 6 (corresponding to Example 4).
- Test Example B The latent curing agent prepared in Example 4 was heat-treated at 120 ° C. for 30 minutes, and the heat-cured latent curing agent was used in the same manner as in Example 4 to prepare a thermosetting resin composition.
- the thermosetting resin composition prepared and obtained was subjected to differential thermal scanning calorimetry in the same manner as in Example 1, and the obtained results are shown in Table 5 and FIG.
- Test Example C A latent curing agent was prepared by repeating Example 4, and further a thermosetting resin composition was prepared using the latent curing agent, followed by heat aging treatment at 55 ° C. for 7 hours, and then About the thermosetting resin composition (The thermosetting resin composition of Test Example A which had been aged at 55 ° C. for 7 hours) was subjected to differential thermal scanning calorimetry in the same manner as in Example 1 and obtained. The results are shown in Table 5 and FIG.
- Test Example D The latent curing agent prepared in Example 4 was heat-treated at 120 ° C. for 30 minutes, and the heat-cured latent curing agent was used in the same manner as in Example 4 to prepare a thermosetting resin composition. Then, heat aging treatment is performed at 55 ° C. for 7 hours, and then a thermosetting resin composition subjected to heat aging treatment (the thermosetting resin composition of Test Example B is aged at 55 ° C. for 7 hours) As in Example 1, differential thermal scanning calorimetry was performed, and the obtained results are shown in Table 5 and FIG.
- the production method of the present invention is useful for the production of a latent curing agent for a thermosetting resin composition that is used when an electronic component such as an IC chip must be bonded to a wiring board without excessive heat shock. It is.
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Abstract
Description
工程(A)
多官能イソシアネート化合物を有機溶剤に溶解させて得た油相を、水に水溶性ポリペプチドと界面活性剤とを溶解させて得た水相に乳化させることにより水中油滴型乳化物を得る工程;
工程(B)
水中油滴型乳化物を加熱することにより油相中の多官能イソシアネート化合物を界面重合させて多孔性樹脂粒子を形成する工程;
工程(C)
多孔性樹脂粒子が分散している界面重合反応液にタンパク質分解酵素を投入し、多孔性樹脂粒子を酵素分解処理する工程;
工程(D)
酵素分解処理を受けた多孔性樹脂粒子を界面重合反応液から回収する工程;及び
工程(E)
回収した多孔性樹脂粒子を、イミダゾール化合物を有機溶剤に溶解して得たイミダゾール化合物溶液と混合し、多孔性樹脂粒子にイミダゾール化合物溶液を浸透させ、多孔性樹脂粒子にイミダゾール化合物が保持されてなる潜在性硬化剤を取得する工程
を有する製造方法を提供する。
工程(A)は、多官能イソシアネート化合物を有機溶剤に溶解させて得た油相を、水に水溶性ポリペプチドと界面活性剤とを溶解させて得た水相に乳化させることにより水中油滴型乳化物を得る工程である。
工程(B)は、工程(A)で調製した水中油滴型乳化物を加熱することにより油相中の多官能イソシアネート化合物を界面重合させて多孔性樹脂粒子を形成する工程である。
工程(C)は、工程(B)で調製された多孔性樹脂粒子が分散している界面重合反応液にタンパク質分解酵素を一度にもしくは少しずつ投入し、多孔性樹脂粒子を酵素分解処理する工程である。この酵素分解処理により、多孔性樹脂粒子の表面又は表面近傍に導入されたポリペプチド構造部が酵素分解され、その結果、多孔性樹脂粒子内部へのイミダゾール化合物溶液の浸透性が向上する。
工程(D)は、工程(C)で酵素分解処理を受けた多孔性樹脂粒子を界面重合反応液から回収する工程である。回収した多孔性樹脂粒子は、更に乾燥処理することが好ましい。回収手法としては特に限定は無く、公知の手法により行うことができる。また、回収した後、水や炭化水素系溶媒等の有機溶媒で洗浄してもよい。乾燥処理は、自然乾燥、真空乾燥などの公知の乾燥手法により行うことができる。回収もしくは乾燥後の多孔性樹脂粒子に対し、一次粒子化のためにジェットミル等を用いて解砕処理を施すことができる。
工程(E)は、工程(D)で得た多孔性樹脂粒子を、イミダゾール化合物を有機溶剤に溶解して得たイミダゾール化合物溶液と混合し、多孔性樹脂粒子にイミダゾール化合物溶液を浸透させ、必要に応じて回収、洗浄、乾燥することにより、多孔性樹脂粒子にイミダゾール化合物が保持されてなる潜在性硬化剤を取得する工程である。
<多孔性樹脂粒子の調製>
蒸留水840質量部と、界面活性剤(ニューレックスR-T、日油(株))0.05重量部と、ゼラチン(AP100微粉、新田ゼラチン(株))8質量部とを、温度計を備えた3リットルの界面重合容器に入れ、均一に混合した。この混合液に、更に、メチレンジフェニル-4,4′-ジイソシアネート(3モル)のトリメチロールプロパン(1モル)付加物(D-109、三井化学(株))150質量部を、酢酸エチル450質量部に溶解した油相を投入し、体積換算平均粒子径が10μm以下となるように、室温で7200rpmのホモジナイザー(T-65D、IKAジャパン(株))を用いて5分間、乳化混合し、水中油滴型乳化物を得た。
得られた実施例1の多孔性樹脂粒子10質量部を、エタノール60質量部に、融点が137~145℃の2-メチルイミダゾール(2MZ-H、四国化成工業(株))40質量部を溶解した溶液100質量部に投入し、30℃で6時間、200rpmで撹拌した。その後、室温で20時間撹拌を続けた。撹拌終了後、イミダゾール化合物の浸透処理が施された多孔性樹脂粒子を濾取し、蒸留水で洗浄後、真空乾燥し、更に、ジェットミル(AO-JET MILL、(株)セイシン企業)で解砕処理をし、一次粒子化した。これにより潜在性硬化剤を得た。
ビスフェノールA型液状エポキシ樹脂(EP828、三菱化学(株))80質量部に、得られた潜在性硬化剤20質量部を、混練機(あわとり練太郎、(株)シンキー)を用いて均一に混合することにより熱硬化型樹脂組成物を得た。
得られた熱硬化型樹脂組成物について、示差熱走査熱量計(DSC)(DSC6200、セイコーインスツル(株))を用いて示差熱走査熱量測定を行った(評価量5mg、昇温速度10℃/分)。得られた結果を表1及び図2に示す。ここで、潜在性硬化剤の硬化特性に関し、発熱開始温度は硬化開始温度を意味しており、発熱ピーク温度は最も硬化が活性となる温度を意味しており、総発熱量は、硬化反応の開始から完結までに発生した熱量を意味している。
2-メチルイミダゾールに代えて、融点が41℃の2-エチル-4-メチルイミダゾール(2E4MZ、四国化成工業(株))を使用すること以外、実施例1と同様にして潜在性硬化剤を調製し、更にそれを用いて熱硬化型樹脂組成物を調製した。得られた熱硬化型樹脂組成物について、実施例1と同様に示差熱走査熱量測定を行い、得られた結果を表1及び図2に示す。
2-メチルイミダゾールに代えて、融点が137~147℃の2-フェニルイミダゾール(2PZ-PW、四国化成工業(株))を使用すること以外、実施例1と同様にして潜在性硬化剤を調製し、更にそれを用いて熱硬化型樹脂組成物を調製した。得られた熱硬化型樹脂組成物について、実施例1と同様に示差熱走査熱量測定を行い、得られた結果を表1及び図2に示す。
2-メチルイミダゾールの配合量40質量部のうちの10質量部を、液状の第三級アミン系硬化促進剤として2,4,6-トリス(ジメチルアミノメチル)フェノール(ルベアック-DMP-30、ナカライテクス(株))に代えること以外、実施例1と同様にして潜在性硬化剤を調製し、更にそれを用いて熱硬化型樹脂組成物を調製した。得られた熱硬化型樹脂組成物について、実施例1と同様に示差熱走査熱量測定を行い、得られた結果を表2及び図3に示す。
2-メチルイミダゾールの配合量40質量部のうちの20質量部を、液状の第三級アミン系硬化促進剤として2,4,6-トリス(ジメチルアミノメチル)フェノール(ルベアック-DMP-30、ナカライテクス(株))に代えること以外、実施例1と同様に潜在性硬化剤を調製し、更にそれを用いて熱硬化型樹脂組成物を調製した。得られた熱硬化型樹脂組成物について、実施例1と同様に示差熱走査熱量測定を行い、得られた結果を表2及び図3に示す。参考のために、併せて実施例1の結果も表2および図3に示す。
2-メチルイミダゾールの配合量40質量部のうちの10質量部を、融点が41℃の2-エチル-4-メチルイミダゾール(2E4MZ、四国化成工業(株))を使用すること以外、実施例1と同様にして潜在性硬化剤を調製し、更にそれを用いて熱硬化型樹脂組成物を調製した。得られた熱硬化型樹脂組成物について、実施例1と同様に示差熱走査熱量測定を行い、得られた結果を表3及び図4に示す。
2-メチルイミダゾールの配合量40質量部のうちの10質量部を、融点が137~147℃の2-フェニルイミダゾール(2PZ-PW、四国化成工業(株))を使用すること以外、実施例1と同様にして潜在性硬化剤を調製し、更にそれを用いて熱硬化型樹脂組成物を調製した。得られた熱硬化型樹脂組成物について、実施例1と同様に示差熱走査熱量測定を行い、得られた結果を表3及び図4に示す。
2-メチルイミダゾールの配合量40質量部のうちの10質量部を、融点が174~184℃の2-フェニル-4-メチルイミダゾール(2P4MZ、四国化成工業(株))を使用すること以外、実施例1と同様にして潜在性硬化剤を調製し、更にそれを用いて熱硬化型樹脂組成物を調製した。得られた熱硬化型樹脂組成物について、実施例1と同様に示差熱走査熱量測定を行い、得られた結果を表3及び図4に示す。参考のために、併せて実施例1の結果も表3および図4に示す。
ゼラチン(AP100微粉、新田ゼラチン(株))8質量部に代えて、ポリビニルアルコール(PVA-205、(株)クラレ)4質量部を使用すること以外は、実施例1と同様にして潜在性硬化剤を調製した。得られた潜在性硬化剤について、熱重量測定-示差熱分析装置(TG-DTA)(TG/DTA6200、セイコーインスツル(株))を用いて、加熱重量減少率を測定(評価量5mg、昇温速度10℃/分)した。得られた結果を表4及び図5に示す。参考のために、併せて、イミダゾール化合物浸透処理前の実施例1で調製した多孔性樹脂粒子、並びに実施例6で調製した潜在性硬化剤についても加熱重量減少率を測定した。得られた結果を表4及び図5に示す。なお、重量減少率は、初期重量に対する、260℃(熱分解開始温度)加熱時の減少重量の割合であり、カプセル化率は、重量減少率からイミダゾール化合物溶液浸透前の実施例1の多孔性樹脂粒子の重量減少率を減じた値である。
試験例A:実施例4を繰り返すことにより潜在性硬化剤を調製し、更にそれを用いて熱硬化型樹脂組成物を調製し、得られた熱硬化型樹脂組成物について、実施例1と同様に示差熱走査熱量測定を行い、得られた結果を表5及び図6に示す(実施例4に相当)。
Claims (13)
- 多官能イソシアネート化合物を界面重合させて得た多孔性樹脂粒子にイミダゾール化合物が保持されてなる潜在性硬化剤の製造方法であって、以下の工程(A)~(E):
工程(A)
多官能イソシアネート化合物を有機溶剤に溶解させて得た油相を、水に水溶性ポリペプチドと界面活性剤とを溶解させて得た水相に乳化させることにより水中油滴型乳化物を得る工程;
工程(B)
水中油滴型乳化物を加熱することにより油相中の多官能イソシアネート化合物を界面重合させて多孔性樹脂粒子を形成する工程;
工程(C)
多孔性樹脂粒子が分散している界面重合反応液にタンパク質分解酵素を投入し、多孔性樹脂粒子を酵素分解処理する工程;
工程(D)
酵素分解処理を受けた多孔性樹脂粒子を界面重合反応液から回収する工程;及び
工程(E)
回収した多孔性樹脂粒子を、イミダゾール化合物を有機溶剤に溶解して得たイミダゾール化合物溶液と混合し、多孔性樹脂粒子にイミダゾール化合物溶液を浸透させ、多孔性樹脂粒子にイミダゾール化合物が保持されてなる潜在性硬化剤を取得する工程
を有する製造方法。 - 工程(A)において、油相が、多官能イソシアネート化合物を1.5~5質量倍の有機溶剤に溶解させたものである請求項1記載の製造方法。
- 水溶性ポリペプチドが、ゼラチンである請求項1記載の製造方法。
- 該ゼラチンとして、JISK6503-2001によるゼリー強度が10~250を示すものを使用する請求項3に記載の製造方法。
- 工程(E)におけるイミダゾール化合物溶液が、更に第三級アミン化合物を含有する請求項1~4のいずれかに記載の製造方法。
- 第三級アミン化合物が、2,4,6-トリス(ジメチルアミノメチル)フェノールを含有する請求項5記載の製造方法。
- イミダゾール化合物が、2種のイミダゾール化合物を含有する請求項1~6のいずれかに記載の製造方法。
- イミダゾール化合物が、融点137~145℃の2-メチルイミダゾールと、それと同等の又はより低い融点を有する別のイミダゾール化合物を含有する請求項7記載の製造方法。
- イミダゾール化合物が、融点137~145℃の2-メチルイミダゾールと、融点41℃の2-エチル-4-メチルイミダゾールまたは融点137~147℃の2-フェニルイミダゾールとを含有する請求項7記載の製造方法。
- 請求項1~9のいずれかの製造方法により得られた潜在性硬化剤と、熱硬化型樹脂とを含有することを特徴とする熱硬化型樹脂組成物。
- 熱硬化型樹脂が熱硬化型エポキシ樹脂である請求項10記載の熱硬化型樹脂組成物。
- 請求項10又は11記載の熱硬化型樹脂組成物中に、異方性導電接続用導電粒子を分散させフィルム化してなる異方性導電接着フィルム。
- 請求項10又は11記載の熱硬化型樹脂組成物をフィルム化してなる太陽電池用接着フィルム。
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CN201180044679.9A CN103249754B (zh) | 2010-09-17 | 2011-07-13 | 潜在性固化剂的制备方法 |
KR1020127014228A KR101780515B1 (ko) | 2010-09-17 | 2011-07-13 | 잠재성 경화제의 제조 방법 |
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KR20220136489A (ko) * | 2012-07-24 | 2022-10-07 | 미쯔비시 케미컬 주식회사 | 도전체, 도전성 조성물, 및 적층체 |
ES2708803T3 (es) * | 2014-10-14 | 2019-04-11 | Henkel Ag & Co Kgaa | Dispersiones acuosas de poliuretano estabilizado con péptido |
US20170369633A1 (en) * | 2014-12-23 | 2017-12-28 | 3M Innovative Properties Company | Curable and cured epoxy resin compositions |
WO2018138069A1 (en) * | 2017-01-24 | 2018-08-02 | Agfa Nv | Capsules stabilised by cationic dispersing groups |
JP7132659B2 (ja) | 2019-03-04 | 2022-09-07 | 株式会社エマオス京都 | 多孔質体および多孔質体の製造方法 |
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JP2006291053A (ja) | 2005-04-12 | 2006-10-26 | Sony Chemical & Information Device Corp | 潜在性硬化剤の製造方法 |
WO2009028224A1 (ja) * | 2007-08-28 | 2009-03-05 | Sony Chemical & Information Device Corporation | マイクロカプセル型潜在性硬化剤 |
JP2011001558A (ja) * | 2010-09-17 | 2011-01-06 | Sony Chemical & Information Device Corp | 潜在性硬化剤の製造方法 |
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US3497524A (en) * | 1967-07-12 | 1970-02-24 | Dexter Corp | Epoxy resins cured with a tertiary amine complex of tetrachloro- or tetrabromophthalic acid |
CA1331904C (en) * | 1987-05-29 | 1994-09-06 | Toshimasa Takata | Epoxy compounds and epoxy resin compositions containing the same |
JP2903327B2 (ja) * | 1990-02-13 | 1999-06-07 | 株式会社スリーボンド | エポキシ樹脂用潜在性硬化剤 |
JP3060452B2 (ja) * | 1995-10-18 | 2000-07-10 | ソニーケミカル株式会社 | 異方性導電接着フィルム |
JP4381255B2 (ja) * | 2003-09-08 | 2009-12-09 | ソニーケミカル&インフォメーションデバイス株式会社 | 潜在性硬化剤 |
US20070166344A1 (en) * | 2006-01-18 | 2007-07-19 | Xin Qu | Non-leaching surface-active film compositions for microbial adhesion prevention |
JP5228644B2 (ja) * | 2007-10-05 | 2013-07-03 | 日立化成株式会社 | エポキシ樹脂用マイクロカプセル型潜在性硬化剤及びその製造方法、一液性エポキシ樹脂組成物並びにエポキシ樹脂硬化物 |
CN101475790B (zh) * | 2008-01-04 | 2012-10-10 | 杨光 | 新型木材胶粘剂及其制备方法 |
JP2010168525A (ja) * | 2008-12-24 | 2010-08-05 | Hitachi Chem Co Ltd | 透明フィルム、この透明フィルムを用いた積層フィルム、無機粒子挟持フィルム、及び、ディスプレイ用パネル |
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JP2006291053A (ja) | 2005-04-12 | 2006-10-26 | Sony Chemical & Information Device Corp | 潜在性硬化剤の製造方法 |
WO2009028224A1 (ja) * | 2007-08-28 | 2009-03-05 | Sony Chemical & Information Device Corporation | マイクロカプセル型潜在性硬化剤 |
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KR101780515B1 (ko) | 2017-09-21 |
TW201213402A (en) | 2012-04-01 |
EP2617751A1 (en) | 2013-07-24 |
CN103249754B (zh) | 2015-05-20 |
TWI494354B (zh) | 2015-08-01 |
JP5601115B2 (ja) | 2014-10-08 |
KR20130108060A (ko) | 2013-10-02 |
JP2010280914A (ja) | 2010-12-16 |
US9481787B2 (en) | 2016-11-01 |
CN103249754A (zh) | 2013-08-14 |
US20120153230A1 (en) | 2012-06-21 |
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