WO2013118697A1 - 硬化性樹脂用靭性改質剤および硬化性樹脂組成物 - Google Patents
硬化性樹脂用靭性改質剤および硬化性樹脂組成物 Download PDFInfo
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- WO2013118697A1 WO2013118697A1 PCT/JP2013/052548 JP2013052548W WO2013118697A1 WO 2013118697 A1 WO2013118697 A1 WO 2013118697A1 JP 2013052548 W JP2013052548 W JP 2013052548W WO 2013118697 A1 WO2013118697 A1 WO 2013118697A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3227—Compounds containing acyclic nitrogen atoms
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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
- C08G59/40—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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/10—Latex
Definitions
- Curable resins represented by phenol resins, unsaturated polyester resins, epoxy resins, and the like are widely used in various fields because of their excellent heat resistance, mechanical strength, dimensional accuracy, and the like.
- a molded product obtained from a curable resin such as an epoxy resin has a problem that it exhibits very brittle properties because of its low fracture toughness.
- a method of adding a rubber component As a method of adding a rubber component, a method of adding a reactive liquid rubber (CTBN or the like) or a nitrile rubber, a method of mixing a core-shell polymer with an epoxy resin, or the like is known.
- CBN reactive liquid rubber
- a nitrile rubber a method of mixing a core-shell polymer with an epoxy resin, or the like.
- the reactive liquid rubber undergoes a process of once dissolving in the epoxy resin and then phase-separating at the time of curing, the morphology of the cured product changes depending on the type of epoxy resin to be blended and the curing conditions, and the desired
- the rubber component partially dissolves and remains in the cured epoxy resin phase. It is known that problems such as a decrease in the quality of epoxy resin products occur due to a decrease in the temperature.
- the primary particle aggregate is, for example, in the form of powder of several tens to several hundreds of microns.
- these are finely powdered to less than 10 ⁇ m, and further heated and stirred at a temperature of 50 to 200 ° C., high-speed shear stirring, hot roll, intermixer, kneader, triple roll, etc. If the kneader is not mixed carefully, there is a problem that the mixed core-shell polymer easily precipitates or floats and is separated.
- Patent Document 1 water is brought into contact with a mixture obtained by mixing an aqueous latex of rubber-like polymer particles with an organic solvent having partial solubility in water, and the rubber-like polymer particles Agglomerates are formed, and the aqueous phase is separated from the mixture of the agglomerates and the aqueous phase to obtain aggregates of rubber-like polymer particles with less impurities, and the dispersion obtained by adding an organic solvent to the aggregates
- a polymerizable organic compound having a reactive group such as an epoxy resin and distilling off a volatile component
- Dispersibility for a curable resin containing a thermoplastic resin and further a dispersibility in a cured product obtained by curing a curable resin, and a toughness modifier for a curable resin excellent in toughness improving effect, and It aims at providing the curable resin composition to contain.
- the present inventors have carried out emulsion polymerization of a vinyl monomer using a nonionic reactive surfactant in the presence of a rubber-like polymer latex. Dispersibility with respect to curable resins containing thermoplastic resins, and dispersibility in cured products obtained by curing curable resins are good, and a toughness modifier for curable resins having an excellent toughness improving effect can be obtained. I found it.
- the present invention relates to a nonionic reactive surfactant containing 5 to 50% by mass of the vinyl monomer (B) in the presence of 50 to 95% by mass (as a rubber polymer component) of the rubber-like polymer (A) latex.
- the present invention relates to a toughness modifier for curable resin (D) obtained by emulsion polymerization using (C) 0.5 to 15 parts by mass (based on (A) and (B) 100 parts by mass).
- the rubber-like polymer (A) contains 50 to 100% by mass of at least one monomer selected from diene monomers and (meth) acrylate monomers, and other copolymerizable vinyl monomers.
- a rubber elastic body composed of 0 to 50% by mass of a polymer, a polysiloxane rubber-based elastic body, or a mixture thereof,
- Vinyl monomer (B) is (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinyl cyanide monomer, unsaturated acid derivative, (meth) acrylic acid amide derivative, and maleimide derivative It is preferable that it consists of 1 or more types chosen from the group which consists of.
- nonionic reactive surfactant (C) is a polyoxyalkylene alkenyl ether.
- Nonionic reactive surfactant (C) is represented by the following general formula (1)
- R is an alkenyl group having a terminal double bond.
- M is 2 to 50, and n is 2 to 100. It is preferable that it is represented by these.
- the toughness modifier has a three-layer structure, rubber-like polymer (A) in the presence of latex, vinyl monomer (B1), and monomer (E) having two or more radically polymerizable groups in one molecule Is preferably obtained by emulsion polymerization of the vinyl monomer (B2) using a nonionic reactive surfactant (C).
- the present invention also relates to a nonionic reactive surfactant containing 5 to 50% by mass of the vinyl monomer (B) in the presence of 50 to 95% by mass (as a rubber polymer component) of the rubber-like polymer (A) latex.
- C A method for producing a toughness modifier for curable resin (D), comprising a step of emulsion polymerization using 0.5 to 15 parts by mass (based on a total of 100 parts by mass of (A) and (B)) About.
- the present invention also relates to a curable resin composition
- a curable resin composition comprising 20 to 99.5% by mass of the curable resin (D) and 0.5 to 80% by mass of the toughness modifier of the present invention.
- the curable resin composition is prepared by mixing an aqueous latex containing a toughness modifier with an organic solvent having a solubility in water at 20 ° C. of 5 to 40% by mass or less, and further mixing with an excess amount of water.
- a first step of slowly aggregating the modifier, and the slowly aggregated toughness modifier is separated from the liquid phase and recovered, and then mixed with an organic solvent again to obtain an organic solvent dispersion of the toughness modifier. It is preferable to prepare by the manufacturing method including the 2nd process to obtain, and the 3rd process of distilling off the said organic solvent, after further mixing the said organic solvent dispersion liquid with the said curable resin (D).
- the curable resin composition further contains a thermoplastic resin (F).
- thermoplastic resin (F) is preferably at least one selected from the group consisting of polyethersulfone, polyetherimide, phenoxy resin, and novolak resin.
- the curable resin composition is preferably a cured product after curing in which a toughness modifier is dispersed in primary particles in a matrix.
- the present invention also relates to a cured product obtained by curing the curable resin composition of the present invention.
- the toughness modifier for curable resin of the present invention has good dispersibility in a matrix of a curable resin and a cured product obtained by curing the curable resin, and further includes a thermoplastic resin. Also shows good dispersibility. In addition, the cured molded body containing the present modifier has excellent toughness.
- the toughness modifier of the present invention is a nonionic reactive agent containing 5 to 50% by mass of the vinyl monomer (B) in the presence of 50 to 95% by mass of a rubber-like polymer (A) latex (as a rubber polymer component).
- the surfactant (C) is obtained by emulsion polymerization using 0.5 to 15 parts by mass (based on a total of 100 parts by mass of (A) and (B)).
- the toughness modifier may have a three-layer structure including a core portion, an intermediate coating layer, and an outermost layer. preferable.
- the particle size of the toughness modifier there is no particular limitation on the particle size of the toughness modifier, and any particle size may be used as long as the toughness modifier can be stably obtained in the state of an aqueous latex.
- the volume average particle diameter is preferably about 0.03 to 2 ⁇ m, more preferably about 0.05 to 1 ⁇ m from the viewpoint of easy production.
- the polymer constituting the rubbery polymer (A) is not particularly limited, but is selected from the group consisting of diene monomers (particularly conjugated diene monomers) and (meth) acrylic acid ester monomers.
- (meth) acryl means acryl and / or methacryl.
- the polymer constituting the rubbery polymer (A) is crosslinked and can swell in a suitable solvent, but does not substantially dissolve.
- the rubbery polymer (A) is insoluble in the curable resin (D).
- the gel content of the rubbery polymer (A) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and most preferably 95% by mass or more.
- the glass transition temperature (Tg) of the polymer constituting the rubbery polymer (A) is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower.
- diene monomer constituting the rubber elastic body examples include conjugated diene monomers such as butadiene, isoprene and chloroprene, but butadiene is particularly preferable from the viewpoints of polymerizability and availability.
- (meth) acrylic acid ester monomers examples include butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, and the like. From the viewpoint of polymerizability and availability, butyl acrylate and 2-ethylhexyl acrylate are used. Is particularly preferred. These can be used alone or in combination of two or more.
- the rubber elastic body may be a copolymer of a diene monomer or a (meth) acrylic acid ester monomer and another vinyl monomer copolymerizable therewith.
- the vinyl monomer copolymerizable with the diene monomer or the (meth) acrylate monomer is selected from the group consisting of aromatic vinyl monomers and vinyl cyanide monomers. Monomer. Examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, and vinyl naphthalene, and examples of the vinyl cyanide monomer include (meth) acrylonitrile and substituted acrylonitrile. These can be used alone or in combination of two or more.
- the amount of one or more monomers selected from the group consisting of diene monomers and (meth) acrylate monomers is preferably 50% by mass or more based on the mass of the entire rubber elastic body, More preferably, it is 60 mass% or more.
- the amount of the monomer used is less than 50% by mass, the toughness improving effect of the toughness modifier of the present invention tends to decrease.
- the amount of the other copolymerizable vinyl monomer used is preferably 50% by mass or less, more preferably 40% by mass or less, based on the mass of the entire rubber elastic body.
- a polyfunctional monomer may be included in order to adjust the degree of crosslinking.
- the polyfunctional monomer include divinylbenzene, butanediol di (meth) acrylate, triallyl (iso) cyanurate, allyl (meth) acrylate, diallyl itaconate, diallyl phthalate, and the like.
- the amount of the polyfunctional monomer used is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less with respect to the mass of the entire rubber elastic body. When the amount used exceeds 10% by mass, the toughness improving effect of the toughness modifier of the present invention tends to decrease.
- a chain transfer agent may be used to adjust the molecular weight and the degree of crosslinking of the polymer constituting the rubber elastic body.
- chain transfer agents include alkyl mercaptans having 5 to 20 carbon atoms.
- the amount of the chain transfer agent used is preferably 5% by mass or less, more preferably 3% by mass or less, based on the mass of the entire rubber elastic body. When the amount of the chain transfer agent used exceeds 5% by mass, the amount of the uncrosslinked component of the rubber elastic body increases, and the heat resistance of the cured curable resin obtained using the toughness modifier of the present invention, There is a possibility of adversely affecting the rigidity.
- the rubber-like polymer (A) it is also possible to use a polysiloxane rubber-based elastic body in place of or in combination with the rubber elastic body.
- a polysiloxane rubber-based elastic body for example, a polysiloxane composed of alkyl or aryl disubstituted silyloxy units such as dimethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, etc. Rubber can be used.
- the rubber polymer (A) can be produced by a known emulsion polymerization method.
- the emulsifier in the aqueous medium it is preferable to use an emulsifier that does not impair the emulsion stability even when the pH of the aqueous latex is neutral.
- alkyl or aryl sulfonic acid such as dioctyl sulfosuccinic acid and dodecyl benzene sulfonic acid, alkyl or aryl ether sulfonic acid, alkyl or aryl sulfuric acid such as dodecyl sulfuric acid, alkyl or aryl ether Sulfuric acid, alkyl or aryl substituted phosphoric acid, alkyl or aryl ether substituted phosphoric acid, N-alkyl or aryl sarcosine acid represented by dodecyl sarcosine acid, alkyl or aryl carboxylic acid represented by oleic acid, stearic acid, etc.
- alkyl or aryl sulfonic acid such as dioctyl sulfosuccinic acid and dodecyl benzene sulfonic acid
- alkyl or aryl ether sulfonic acid
- alkali metal salts or ammonium salts of various acids such as acids, alkyl or aryl ether carboxylic acids, and nonionic emulsifiers such as alkyl or aryl substituted polyethylene glycols. These can be used alone or in combination of two or more.
- emulsifiers can be used in the rubbery polymer (A) latex production process as little as possible as long as the dispersion stability is not hindered in the gist of the preferred embodiment of the present invention. preferable.
- polymerization initiator known initiators such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate and the like can be used as the thermal decomposition type initiator.
- Organic peroxides such as t-butylperoxyisopropyl carbonate, paramentane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-hexyl peroxide, etc.
- Oxides such as inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate; reducing agents such as sodium formaldehyde sulfoxylate and glucose as necessary; and iron sulfate (II as necessary) ),
- a chelating agent such as disodium ethylenediaminetetraacetate if necessary, and a redox initiator using a phosphorus-containing compound such as sodium pyrophosphate if necessary.
- the polymerization can be performed at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set in a wide range, which is preferable.
- organic peroxides such as cumene hydroperoxide, dicumyl peroxide, and t-butyl hydroperoxide are preferably used as the redox initiator.
- the amount of the initiator used or a redox type initiator is used, the amount of the reducing agent, transition metal salt, chelating agent or the like used can be within a known range.
- a known chain transfer agent can be used within a known use range.
- a known surfactant can be used within a known use range.
- the polymerization temperature, pressure, deoxygenation, and other conditions during the polymerization can be within the known ranges.
- the vinyl monomer (B) used in the present invention is (meth) acrylic acid because it can be obtained at a low cost and can have both good graft polymerizability and affinity for a curable resin. It is preferably at least one selected from the group consisting of ester monomers, aromatic vinyl monomers, vinyl cyanide monomers, unsaturated acid derivatives, (meth) acrylic acid amide derivatives, and maleimide derivatives. .
- Reactive side chains such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyalkyl (meth) acrylate, and epoxyalkyl (meth) acrylate as (meth) acrylic acid ester monomers
- (meth) acrylic acid esters having a formula for example, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, etc.
- aromatic vinyl monomer include styrene and ⁇ -methylstyrene.
- An example of the vinyl cyanide monomer is (meth) acrylonitrile.
- Examples of the unsaturated acid derivative include ⁇ , ⁇ -unsaturated acids such as (meth) acrylic acid and maleic anhydride, and ⁇ , ⁇ -unsaturated acid anhydrides.
- Examples of (meth) acrylic acid amide derivatives include (meth) acrylamide (including N-substituted products).
- maleimide derivative maleic imide can be exemplified. These can be used alone or in combination of two or more.
- the vinyl monomer (B1) and vinyl monomer (B2) used for the production of the toughness modifier having a three-layer structure are also selected from the compounds used as the vinyl monomer (B). Can do.
- styrene is preferred as the vinyl monomer (B1) from the viewpoint of preventing impregnation of the vinyl monomer (B2) into the rubber polymer layer and affinity with the curable resin.
- the vinyl monomer (B2) is preferably styrene, methyl methacrylate, acrylonitrile, or glycidyl methacrylate.
- the polymerization part ratio (mass ratio) of the rubber-like polymer (A) / vinyl monomer (B) is preferably in the range of 50/50 to 95/5, more preferably 60/40 to 90/10. It is. When the ratio of the polymerization part (A) / (B) is out of 50/50 and the ratio of (A) is lowered, the effect of improving toughness tends to be lowered. If the ratio of (B) deviates from 95/5, the dispersibility in the curable resin decreases, and the expected physical properties may not be obtained.
- the mass of the rubber-like polymer (A) / (total of the masses of the vinyl monomer (B1) and the vinyl monomer (B2)) is in the above range. It is preferable to be within.
- the polymerization ratio (mass ratio) of vinyl monomer (B1) for forming the intermediate coating layer / vinyl monomer (B2) for forming the outermost layer is preferably 10/90 to 90/10, 30 / 70 to 80/20 is more preferable. If the polymerization ratio falls outside 10/90 and the ratio of (B1) decreases, the contribution to the improvement of dispersibility may be reduced. When the polymerization ratio is out of 90/10 and the ratio of (B2) is lowered, there is a possibility that the effect of toughness modification cannot be obtained.
- Nonionic reactive surfactant (C) The toughness modifier for a curable resin of the present invention is obtained by emulsion polymerization of a vinyl monomer (B) using a nonionic reactive surfactant in the presence of the rubber-like polymer (A) latex. Therefore, the desired dispersibility and toughness-improving effect can be exhibited in the curable resin or the curable resin composition containing the curable resin and the thermoplastic resin and the cured product thereof.
- the nonionic reactive surfactant used in the present invention is a nonionic interface such as an ester type, an ether type or an ester / ether type having a radically polymerizable unsaturated group such as an acryloyl group, a methacryloyl group or an alkenyl group.
- An activator can be used.
- polyoxyalkylene alkenyl ethers are preferable from the viewpoint of polymerization stability and hydrolysis resistance, and nonionic reactive surfactants represented by the following general formula (1) are particularly preferable.
- R is an alkenyl group having a terminal double bond.
- M is 2 to 50, and n is 2 to 100.
- m is preferably 2 to 40, and more preferably 2 to 30.
- n is preferably from 5 to 80, and more preferably from 10 to 70.
- m —C 4 H 8 O— units and n —C 2 H 4 O— units may be located at any position in the main chain. That is, there is no particular limitation on the order of arrangement of the —C 4 H 8 O— units and —C 2 H 4 O— units in the main chain of the general formula (1), and the polymer main chain may be a block copolymer or a random copolymer. Alternatively, it may be a random copolymer including a block copolymer portion.
- the minimum of the usage-amount of a nonionic reactive surfactant is 0.5 mass part with respect to a total of 100 mass parts of a rubber-like polymer (A) and a vinyl monomer (B), and 1 mass part is more. Preferably, 1.5 parts by weight is more preferable.
- the amount of the nonionic reactive surfactant used is less than 0.5 parts by mass, the effect of stabilizing the dispersion with respect to the curable resin containing the thermoplastic resin may not be obtained.
- an upper limit is 15 mass parts, 13 mass parts is more preferable, and 11 weight part is still more preferable. If the amount of the nonionic reactive surfactant used exceeds 15 parts by mass, the amount of unreacted surfactant increases, which may adversely affect the mechanical properties and wet heat characteristics of the curable resin composition.
- Examples of the monomer (E) having two or more radical polymerizable groups used in the production of a toughness modifier having a three-layer structure include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, triallyl (iso) cyanurate, diallyl phthalate, divinylbenzene, diallyl itaconate, etc. It is done. Of these, allyl methacrylate or triallyl isocyanurate is preferable from the viewpoints of polymerizability and availability. These can be used alone or in combination of two or more.
- the lower limit of the amount of the monomer (E) having two or more radical polymerizable groups is preferably 0.1 parts by mass, more preferably 0.3 parts by mass with respect to 100 parts by mass of the vinyl monomer (B1). 0.5 parts by mass is particularly preferable.
- the upper limit is preferably 10 parts by mass, more preferably 8 parts by mass, and particularly preferably 5 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving dispersibility with respect to the curable resin described later and the curable resin containing the thermoplastic resin may not be exhibited. If it exceeds 10 parts by mass, the toughening effect may be reduced.
- the toughness modifier of the present invention can be produced by a known emulsion polymerization method.
- the emulsion polymerization of the vinyl monomer (B) to the rubber-like polymer (A) latex, as described above, except that the nonionic reactive surfactant (C) is used as the surfactant it is known.
- the same polymerization method as the polymerization method of the rubbery polymer (A) can be applied.
- Polymerization may be performed in one stage or in two or more stages.
- a rubber-like is added to the reactor in which the vinyl monomer (B) is charged in advance
- a method of performing polymerization after adding the latex of the polymer (A) can be employed.
- the toughness modifier having a three-layer structure can be produced by the same method as above except that it includes a step of forming an intermediate coating layer.
- an intermediate coating layer is formed by polymerizing a vinyl monomer (B1) and a monomer (E) having two or more radical polymerizable groups in one molecule in the presence of a rubber-like polymer (A) latex.
- a method of forming the outermost layer by emulsion polymerization of the vinyl monomer (B2) using the nonionic reactive surfactant (C) can be mentioned.
- the curable resin composition of the present invention contains 20 to 99.5% by mass of the curable resin (D) and 0.5 to 80% by mass of the toughness modifier of the present invention. If the content of the toughness modifier is less than 0.5% by mass, there is a problem that the toughness is not sufficiently modified, and if it is more than 80% by mass, the curable resin composition is too soft.
- the content is preferably 0.7% by mass or more, and more preferably 1.0% by mass or more. Moreover, it is preferable that it is 45 mass% or less, and it is more preferable that it is 40 mass% or less.
- thermosetting resin and optical (electron beam) curable resin can be used.
- a reactive polymer (or monomer) having a double bond, a methylol group, a cyclic ether, a cyanate group or the like can be mentioned.
- Examples of the reactive polymer (monomer) having a double bond include unsaturated polyester resins, vinyl ester resins, and acrylate resins.
- Examples of the reactive polymer (monomer) having a methylol group include a phenol resin.
- Examples of the reactive polymer (monomer) having a cyclic ether include an epoxy resin and an oxetane resin.
- Examples of the reactive monomer having a cyanate group include a cyanate ester resin.
- curable resins (D) unsaturated polyester resins, vinyl ester resins, acrylate resins, phenol resins, epoxy resins, and cyanate ester resins are classified as thermosetting resins.
- Epoxy resins, oxetane resins, and acrylate resins are classified as light (electron beam) curable resins.
- thermoplastic resin (F) mentioned later in curable resin you may mix or melt
- the curable resin composition further contains a thermoplastic resin (F).
- the resin component is preferably a mixture of a curable resin and a thermoplastic resin or a dissolved material.
- thermoplastic resin (F) acrylic polymer, polystyrene resin, polycarbonate, polyarylate, polyamide, polyamideimide, polysulfone, polyethersulfone, polyfelsulfone, polyetherketone, polyphenylene sulfide, polyetherimide, polyesterimide, (Modified) Polyphenylene oxide, resins having phenolic hydroxyl groups, phenoxy resins, novolac resins, and the like.
- Phenoxy resin is a general term for polymers whose main chain is linked by a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether.
- the novolak resin is a polycondensate of phenols, and examples thereof include a phenol novolak resin, a bisphenol novolak resin, and a cresol novolak resin. Among these, it is preferable that it is 1 or more types chosen from the group which consists of polyethersulfone, polyetherimide, a phenoxy resin, and a novolak resin from a heat resistant and affinity viewpoint with curable resin.
- the addition amount of the thermoplastic resin (F) is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and preferably 50 parts by mass or less, and 30 parts by mass or less with respect to 100 parts by mass of the curable resin. Is more preferable. If the amount is less than 2 parts by mass, the effect of improving toughness may not be expected. If the amount exceeds 50 parts by mass, handling may be difficult due to an increase in viscosity.
- the curable resin composition of the present invention can be prepared by the method described in International Publication No. WO2005 / 28546. Specifically, an aqueous latex containing a toughness modifier (specifically, a reaction mixture after producing the toughness modifier by emulsion polymerization) has a solubility in water at 20 ° C. of 5 to 40% by mass or less.
- a toughness modifier specifically, a reaction mixture after producing the toughness modifier by emulsion polymerization
- the organic solvent After mixing with an organic solvent, further mixing with excess water to slowly aggregate the toughness modifier, and after separating and recovering the slowly aggregated toughness modifier from the liquid phase, the organic solvent again And a second step of obtaining an organic solvent dispersion of the toughness modifier, a third step of further distilling off the organic solvent after further mixing the organic solvent dispersion with the curable resin (D), It is preferable to prepare by the manufacturing method containing.
- the first step includes an operation of mixing an aqueous latex with an organic solvent having a solubility in water at 20 ° C. of preferably 5% by mass or more and 40% by mass or less (more preferably 30% by mass or less).
- an organic solvent having a solubility in water at 20 ° C. of preferably 5% by mass or more and 40% by mass or less (more preferably 30% by mass or less).
- solubility of the organic solvent When the solubility of the organic solvent is less than 5% by mass, mixing with the aqueous medium dispersion containing the toughness modifier may be somewhat difficult. When the solubility exceeds 40% by mass, it may be difficult to separate and recover the toughness modifier (described later) from the liquid phase (mainly the aqueous phase) in the second step.
- Examples of the organic solvent having a solubility in water at 20 ° C. of 5% by mass or more and 40% by mass or less include ketones such as methyl ethyl ketone, esters such as methyl formate, methyl acetate, and ethyl acetate, diethyl ether, ethylene glycol diethyl ether, Examples include ethers such as tetrahydropyran, acetals such as methylal, alcohols such as n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol. These organic solvents may be used alone or in combination of two or more.
- the organic solvent used in the first step may be a mixed organic solvent as long as the solubility in water at 20 ° C. is 5% by mass or more and 40% by mass or less as a whole.
- ketones such as methyl propyl ketone, diethyl ketone, methyl isobutyl ketone and ethyl butyl ketone
- esters such as diethyl carbonate, butyl formate, propyl acetate and butyl acetate
- ethers such as diisopropyl ether and dibutyl ether, pentane and hexane
- Aliphatic hydrocarbons such as heptane and octane
- aromatic hydrocarbons such as benzene, toluene and xylene
- halogenated hydrocarbons such as methylene chloride and chloroform, and acetone, cyclohexanone, etc.
- the organic solvent used in the first step is preferably one having a specific gravity lighter than water from the viewpoint of facilitating removal of the liquid phase (mainly the aqueous phase) in the second step described later.
- the mixing amount of the organic solvent mixed with the aqueous latex is preferably 50 parts by mass or more, more preferably 60 parts by mass or more with respect to 100 parts by mass of the aqueous latex. Further, it is preferably 300 parts by weight or less, more preferably 250 parts by weight or less, and still more preferably 150 parts by weight or less.
- the mixing amount of the organic solvent is less than 50 parts by mass, it may be difficult to form an aggregate of the toughness modifier contained in the aqueous latex.
- the mixing amount of the organic solvent exceeds 300 parts by mass, the amount of water required for obtaining a toughness modifier slow aggregate thereafter increases, and the production efficiency may decrease.
- a well-known thing can be used for mixing operation of the said aqueous latex and an organic solvent.
- a general apparatus such as a stirring tank with a stirring blade may be used, or a static mixer (static mixer), a line mixer (a system in which a stirring apparatus is incorporated in a part of piping), or the like may be used.
- the first step includes an operation of adding and mixing excess water after the operation of mixing the aqueous latex and the organic solvent. Thereby, it will phase-separate and the aggregate of a toughness modifier can be obtained in a loose state.
- the electrolyte such as the water-soluble emulsifier or dispersant, the water-soluble polymerization initiator, or the reducing agent used in the preparation of the aqueous latex can be eluted into the aqueous phase.
- the amount of water mixed is preferably 40 parts by mass or more, and more preferably 60 parts by mass or more with respect to 100 parts by mass of the organic solvent used when mixing with the aqueous latex. Moreover, it is preferable that it is 1000 mass parts or less, and it is more preferable that it is 700 mass parts or less. If the mixing amount of water is less than 40 parts by mass, it may be difficult to obtain the toughness modifier as a slow aggregate. In addition, when the amount of water exceeds 1000 parts by mass, the concentration of the organic solvent in the aggregated toughness modifier is lowered, so that the aggregated toughness modifier is redispersed in the second step described later. The dispersibility of the toughness modifier may decrease, for example, the time required may be prolonged.
- the second step includes an operation of separating and recovering the slowly aggregated toughness modifier from the liquid phase to obtain the toughness modifier dope.
- water-soluble impurities such as an emulsifier can be separated and removed from the toughness modifier.
- the aggregated toughness modifier generally has a floating property with respect to the liquid phase.
- the method include discharging the liquid phase (mainly the aqueous phase) from the bottom of the stirring tank, and filtering using a filter paper, a filter cloth, or a metal screen having a relatively wide opening.
- the amount of the organic solvent contained in the toughness modifier's slow aggregate (toughness modifier dope) is preferably 30% by mass or more, and 35% by mass or more based on the mass of the entire slow agglomerate. Is more preferable. Moreover, it is preferable that it is 95 mass% or less, and it is more preferable that it is 90 mass% or less.
- the content of the organic solvent is less than 30% by mass, it takes a long time to re-disperse the toughness modifier dope in the organic solvent (described later), or irreversible aggregates are likely to remain. Inconvenience may occur. Further, when the content of the organic solvent exceeds 95% by mass, a large amount of water dissolves and remains in the organic solvent, which causes the toughness modifier to aggregate in the third step. There is.
- the amount of the organic solvent contained in the aggregate of the toughness modifier was determined by drying the aggregate of the toughness modifier at 120 ° C. for 15 minutes, and the reduced amount of the organic solvent contained in the aggregate. It is calculated by taking the quantity.
- the second step further includes an operation of mixing the aggregate of toughness modifier (toughness modifier dope) with an organic solvent. Since the toughness modifier aggregates in a gradual state, the toughness modifier can be easily redispersed in the state of primary particles in the organic solvent by mixing with the organic solvent.
- Examples of the organic solvent used in the second step include the organic solvents exemplified as those that can be used in the first step. By using such an organic solvent, water contained in the toughness modifier can be removed by azeotropic distillation with water when the organic solvent is distilled off in the third step described later. Further, the organic solvent used in the second step may be the same as or different from the organic solvent used in the first step.
- the amount of the organic solvent used in the second step is preferably 40 parts by mass or more and more preferably 200 parts by mass or more with respect to 100 parts by mass of the aggregate of the toughness modifier. Moreover, it is preferable that it is 1400 mass parts or less, and it is more preferable that it is 1000 mass parts or less.
- the amount of the organic solvent mixed is less than 40 parts by mass, the toughness modifier is difficult to uniformly disperse in the organic solvent, and the aggregated toughness modifier remains as a lump, or the viscosity increases and the handling becomes difficult. There is a case.
- the amount of the organic solvent mixed exceeds 1400 parts by mass, a large amount of energy and a large-scale apparatus are required for evaporating and distilling the organic solvent in the third step described later, which is uneconomical.
- the aggregated toughness modifier is separated and recovered from the liquid phase between the first step and the second step, and again mixed with an organic solvent having a solubility in water at 20 ° C. of 5% by mass to 40% by mass Furthermore, it is preferable to perform the operation of mixing with excess water to obtain a slow aggregate of the toughness modifier at least once. In addition, this makes it possible to lower the remaining amount of water-soluble impurities such as emulsifiers contained in the toughness modifier dope.
- the third step includes an operation of replacing the organic solvent in the organic solvent solution (organic solvent dispersion) of the toughness modifier obtained in the second step with the curable resin.
- a toughness modifier-dispersed composition in which the toughness modifier is dispersed in the state of primary particles can be obtained. Further, water remaining in the aggregate of the toughness modifier can be distilled off azeotropically.
- a well-known method is applicable as a method of distilling off the organic solvent.
- a method of charging a mixture of an organic solvent solution (dispersion) and the curable resin into a tank and heating and depressurizing it a method of countercurrently contacting a dry gas and the mixture in the tank, and a thin film evaporator
- a continuous method as used, a method using an extruder equipped with a devolatilization mechanism or a continuous stirring tank, and the like.
- Conditions such as temperature and required time for distilling off the organic solvent can be appropriately selected within a range that does not impair the quality of the obtained toughness modifier dispersion composition.
- the amount of the volatile component remaining in the toughness modifier dispersion composition can be appropriately selected within a range where there is no problem depending on the purpose of use of the toughness modifier dispersion composition.
- the preparation method is a cure containing a toughness modifier according to the preparation method of the curable resin composition described above.
- the thermoplastic resin (F) is added and mixed while heating if necessary, or a mixture in which the curable resin and the thermoplastic resin (F) are separately heated or dissolved.
- a curable resin composition comprising a curable resin, a toughness modifier, and a thermoplastic resin (F) can be obtained by adding and mixing the product to the curable resin composition.
- the curable resin mixed with the thermoplastic resin and the curable resin in which the toughness modifier is dispersed may be the same or different.
- the thermoplastic resin (F) is preferably compatible with the curable resin.
- an organic peroxide In the curable resin composition of the present invention, an organic peroxide, a curing accelerator, a chain transfer agent, a photosensitizer, a reducing agent, a plasticizer, a filler, an adhesiveness imparting agent (primer is added as necessary. Including), dyes, pigments, stabilizers, ultraviolet absorbers, diluents (reactive / non-reactive), organic solvents, and the like.
- the cured product of the present invention is obtained by curing the curable resin composition of the present invention. What is necessary is just to select suitably the method of hardening
- a curing agent may be added to the curable resin composition.
- curing agents include amine curing agents such as aliphatic diamines and aromatic diamines; acid anhydrides such as hexahydrophthalic anhydride; novolac-type phenolic resins, imidazole compounds, tertiary amines, triphenylphosphine, aliphatic polyamines.
- Aromatic polyamine polyamide, polymercaptan, dicyandiamide, dibasic acid dihydrazide, N, N′-dialkylurea derivative, N, N′-dialkylthiourea derivative, alkylaminophenol derivative, melamine, guanamine and the like.
- These curing agents may be used alone or in combination of two or more.
- photopolymerization initiators include benzophenone, benzoin methyl ether, methyl-O-benzoylbenzoate, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-methyl- Photo radical polymerization initiators such as 1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2,4-diethylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; hexafluoroantimonate, Examples include onium salts such as aromatic sulfonium salts and aromatic iodonium salts with anions such as hexafluorophosphate and tetraphenylborate, and photocationic polymerization initiators (photoacid
- the curable resin composition of the present invention is preferably a cured product obtained by curing the curable resin composition, in which a toughness modifier is dispersed in primary particles in a matrix (resin).
- a toughness modifier is dispersed in primary particles in a matrix (resin).
- the toughness modifier “primary particle dispersed” means that the toughness modifier particles do not aggregate with each other in the matrix and are dispersed independently of each other, Specifically, it means that the particle dispersion rate is 50% or more.
- the particle dispersion rate (%) is calculated using the following formula 1 by the method described later. From the viewpoint of improving the toughness, the particle dispersion rate is preferably 70% or more, more preferably 75% or more, and further preferably 90% or more.
- the calculated B 1 is calculated by the above equation (equation 1).
- a sample in which B 0 is at least 10 or more and an observation region are selected.
- the curable resin composition of the present invention comprises a molding material, an adhesive, a fiber or filler reinforced composite material, a sealing material, a casting material, an insulating material, a coating material, a filler, a photomolding material, an optical component, ink, and toner. Is preferably used.
- the molding method for example, transfer molding method, casting molding method, coating baking method, rotational molding method, photo-molding method, hand layup molding method combined with carbon fiber, glass fiber, etc., prepreg molding method, A pultrusion molding method, a filament winding molding method, a press molding method, a resin transfer molding (RTM, VaRTM) molding method, an SMC molding method, and the like can be applied, but are not limited thereto.
- the raw materials used in the present production examples, examples and comparative examples are as follows.
- a bisphenol A type liquid epoxy resin manufactured by Mitsubishi Chemical Corporation, product name: jER 828EL
- a modified aromatic amine was used as the curing agent C1.
- thermoplastic resin D1 As the thermoplastic resin D1, a polyether sulfone resin (Sumitomo Chemical Co., Ltd., SUMIKAEXCEL PES 5003P) was used.
- Nonionic reactive surfactant E1 As the nonionic reactive surfactant E1, polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, LATEMUL PD450) was used.
- evaluation methods The evaluation methods in the examples and production examples are as follows.
- Particle dispersion state The freezing fracture surface in liquid nitrogen of the test piece used in the flexural modulus measurement described later is observed at a magnification of 20,000 using a scanning electron microscope (JEOL Ltd., JSM-6300F). The dispersion state was determined using the particle dispersion rate (%) by the following method as an index. Good: Particle dispersion is 70% or more. Poor: The particle dispersion rate is less than 70%.
- the volume average particle size was measured with a particle size measuring device (Microtrac UPA manufactured by Nikkiso Co., Ltd.).
- the cured plate sample was cut into a test piece having a length of 2.5 inches, a width (b) of 0.5 inches, and a thickness (h) of 5 mm, and then a V-notch was formed by a notching machine. Thereafter, a crack was made from the tip of the V notch to the center of the test piece using a razor blade. After curing the test piece at 23 ° C., a three-point bending test was performed using Autograph AG-2000E (manufactured by Shimadzu Corporation) at a distance between supporting points (L) of 50 mm and a test speed of 1 mm / min.
- Autograph AG-2000E manufactured by Shimadzu Corporation
- the fracture toughness value K1c (MPa ⁇ m 1/2 ) was calculated according to the following formulas 3 and 4.
- a is the sum of the depth of the V notch and the length from the V notch tip to the crack tip, and L, h, a, and b are in cm.
- Polymerization was initiated by adding 0.015 parts by mass of paramentane hydroperoxide (PHP) and then 0.04 parts by mass of sodium formaldehyde sulfoxylate (SFS). Four hours after the start of polymerization, 0.01 parts by weight of PHP, 0.0015 parts by weight of EDTA and 0.001 parts by weight of Fe were added. At 10 hours of polymerization, the residual monomer was removed by devolatilization under reduced pressure to complete the polymerization, and latex (R-1) containing polybutadiene rubber particles was obtained. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 0.08 ⁇ m.
- aqueous latex L-3 containing a toughness modifier.
- the polymerization conversion rate of the monomer component was 99% or more.
- the volume average particle diameter of the toughness modifier contained in the obtained aqueous latex was 0.10 ⁇ m.
- curable resin (B1) was added to this organic solvent dispersion so that the toughness modifier / curable resin was 25/75, and after mixing, the organic solvent was distilled off under reduced pressure to disperse the toughness modifier. Obtained as a curable resin (B1) dispersion A1-1. Similarly, by using the curable resin (B2), a curable resin (B2) dispersion A1-2 in which the toughness modifier was dispersed was obtained.
- MEK methyl ethyl ketone
- the curable resin (B1) dispersion A3-1 in which the toughness modifier is dispersed and the curable resin ( B2) Dispersion A3-2 was obtained.
- curable resin (B1) was added to this organic solvent dispersion so that the toughness modifier / curable resin was 25/75, and after mixing, the organic solvent was distilled off under reduced pressure to disperse the toughness modifier. Obtained as curable resin (B1) dispersion A2-1. Similarly, by using the curable resin (B2), a curable resin (B2) dispersion A2-2 in which the toughness modifier was dispersed was obtained.
- the curable resin (B1) dispersion A4-1 in which the toughness modifier was dispersed and the curable resin ( B2) Dispersion A4-2 was obtained.
- the toughness modifier curable resin dispersions obtained in Production Examples 6 and 7 are summarized in Table 1.
- Examples 1 to 4, Comparative Examples 1 to 6) At the mixing ratios shown in Tables 2 and 3, the curable resin and the thermoplastic resin were heated to 120 ° C. while stirring and mixed uniformly. To this uniform mixture, a curable resin dispersion of a toughness modifier and a curing agent are added at a blending ratio shown in Tables 2 and 3 and then mixed well, and then defoamed to obtain a curable resin composition. Obtained.
- This curable resin composition was poured between two glass plates sandwiching a spacer having a thickness of 5 mm, and cured in a hot air oven at 100 ° C. for 2 hours and subsequently at 175 ° C. for 4 hours to obtain a cured plate having a thickness of 5 mm. .
- Tables 2 and 3 show the particle dispersion state, flexural modulus, and K1c results for each cured plate.
- Examples 5 and 6, Comparative Examples 7 and 8) At the mixing ratios shown in Tables 2 and 3, the curable resin and the thermoplastic resin were heated to 120 ° C. while stirring and mixed uniformly. To this uniform mixture, a curable resin dispersion of a toughness modifier and a curing agent are added at a blending ratio shown in Tables 2 and 3 and then mixed well, and then defoamed to obtain a curable resin composition. Obtained.
- This curable resin composition was poured between two glass plates sandwiching a spacer having a thickness of 5 mm, and cured in a hot air oven at 150 ° C. for 1 hour and then at 180 ° C. for 2 hours to obtain a cured plate having a thickness of 5 mm. .
- Tables 2 and 3 show the particle dispersion state, flexural modulus, and K1c results for each cured plate.
- the toughness modifier of the present invention is excellent in dispersibility in a curable resin containing a thermoplastic resin, and the curable resin composition of the present invention is excellent in physical properties after curing. Recognize.
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Abstract
Description
ビニル単量体(B)が、(メタ)アクリル酸エステル単量体、芳香族ビニル単量体、シアン化ビニル単量体、不飽和酸誘導体、(メタ)アクリル酸アミド誘導体、および、マレイミド誘導体からなる群から選ばれる1種以上からなることが好ましい。
で表されるものであることが好ましい。
本発明の靭性改質剤は、ゴム状重合体(A)ラテックス50~95質量%(ゴム重合体成分として)存在下、ビニル単量体(B)5~50質量%を、ノニオン系反応性界面活性剤(C)0.5~15質量部((A)および(B)の合計100質量部に対し)を用いて乳化重合して得られるものである。
ゴム状重合体(A)を構成するポリマーとしては特に限定されないが、ジエン系単量体(特に共役ジエン系単量体)および(メタ)アクリル酸エステル系単量体からなる群より選ばれる1種以上の単量体50~100質量%、ならびに、他の共重合可能なビニル単量体0~50質量%から構成されるゴム弾性体、ポリシロキサンゴム系弾性体、または、これらの混合物であることが好ましい。
なお、本明細書において「(メタ)アクリル」とは、アクリルおよび/またはメタクリルを意味する。
本発明で使用するビニル単量体(B)としては、安価に入手でき、また、良好なグラフト重合性と、硬化性樹脂に対する親和性の双方を可能にできるという点から、(メタ)アクリル酸エステル単量体、芳香族ビニル単量体、シアン化ビニル単量体、不飽和酸誘導体、(メタ)アクリル酸アミド誘導体、および、マレイミド誘導体からなる群より選ばれる1種以上であることが好ましい。
(メタ)アクリル酸エステル単量体としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレートや、ヒドロキシアルキル(メタ)アクリレート、エポキシアルキル(メタ)アクリレート等の反応性側鎖を有する(メタ)アクリル酸エステル類(たとえば、2-ヒドロキシエチル(メタ)アクリレート、グリシジル(メタ)アクリレート等)を例示することができる。
芳香族ビニル単量体としては、スチレン、α-メチルスチレンを例示することができる。
シアン化ビニル単量体としては、(メタ)アクリロニトリルを例示することができる。
不飽和酸誘導体としては、(メタ)アクリル酸、マレイン酸無水物等のα,β-不飽和酸及びα,β-不飽和酸無水物を例示することができる。
(メタ)アクリル酸アミド誘導体としては、(メタ)アクリルアミド(N-置換物を含む)を例示することができる。
マレイミド誘導体としては、マレイン酸イミドを例示することができる。
これらは1種或いは2種以上を適宜組み合わせて使用できる。
特にシェル部に硬化性樹脂硬化時における化学反応性を求める場合には、上記反応性側鎖を有する(メタ)アクリル酸エステル類、(メタ)アクリルアミド(N-置換物を含む)、α,β-不飽和酸、α,β-不飽和酸無水物、マレイミド誘導体、及び、エポキシアルキルビニルエーテル(グリシジルビニルエーテル等)からなるモノマー群より選ばれる1種以上の成分を使用することが好ましい。
中でも、ゴム重合体層へのビニル単量体(B2)の含浸防止、硬化性樹脂に対する親和性の観点から、ビニル単量体(B1)としては、スチレンが好ましい。また、良好なグラフト重合性、硬化性樹脂に対する親和性の観点から、ビニル単量体(B2)としては、スチレン、メチルメタクリレート、アクリロニトリル、グリシジルメタクリレートが好ましい。
本発明の硬化性樹脂用靱性改質剤は、前記のゴム状重合体(A)ラテックス存在下、ノニオン系反応性界面活性剤を用いてビニル系単量体(B)を乳化重合することで得られるため、硬化性樹脂、または、硬化性樹脂および熱可塑性樹脂を含有する硬化性樹脂組成物やその硬化物において所望の分散性ならびに靱性改質効果を発揮できる。
mは2~40であることが好ましく、2~30であることがより好ましい。nは5~80であることが好ましく、10~70であることがより好ましい。
三層構造を有する靱性改質剤の製造に使用されるラジカル重合性基を2以上有する単量体(E)としては、例えば、アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート、トリアリル(イソ)シアヌレート、ジアリルフタレート、ジビニルベンゼン、イタコン酸ジアリル、などが挙げられる。中でも、重合性、入手性の観点から、アリルメタクリレート、又は、トリアリルイソシアヌレートが好ましい。これらは1種類または2種類以上を組み合わせて使用できる。
本発明の靱性改質剤の製造にあたっては、公知の乳化重合法で製造することができる。
ゴム状重合体(A)ラテックスへの、ビニル単量体(B)の乳化重合に際しては、前記の通り、界面活性剤としてノニオン系反応性界面活性剤(C)を使用すること以外は、公知の乳化重合法を適応でき、具体的には、前記ゴム状重合体(A)の重合方法と同様の重合法を適応できる。
本発明の硬化性樹脂組成物は、硬化性樹脂(D)20~99.5質量%、および、本発明の靭性改質剤0.5~80質量%を含有する。
靭性改質剤の含有率が0.5質量%未満であると十分に靭性が改質されないという問題があり、80質量%より多いと硬化性樹脂組成物が軟化しすぎるという問題がある。含有率は、0.7質量%以上であることが好ましく、1.0質量%以上であることがより好ましい。また、45質量%以下であることが好ましく、40質量%以下であることがより好ましい。
本発明で使用する硬化性樹脂(D)としては、特に限定されず、熱硬化性樹脂や光(電子線)硬化性樹脂を使用することができる。例えば、二重結合、メチロール基、環状エーテル、シアナート基等を有する反応性ポリマー(もしくはモノマー)が挙げられる。
硬化性樹脂組成物は、更に熱可塑性樹脂(F)を含有することが好ましい。硬化性樹脂組成物に靱性を付与する目的から、樹脂成分は、硬化性樹脂と熱可塑性樹脂の混合物、または、溶解物であることが好適である。
本発明の硬化性樹脂組成物は、国際公開第WO2005/28546号パンフレットに記載の方法により調製することができる。具体的には、靱性改質剤を含有する水性ラテックス(詳細には、乳化重合によって靱性改質剤を製造した後の反応混合物)を、20℃における水に対する溶解度が5~40質量%以下の有機溶媒と混合した後、更に過剰の水と混合して、靱性改質剤を緩凝集させる第1工程と、緩凝集した靱性改質剤を液相から分離して回収した後、再度有機溶媒と混合して、靱性改質剤の有機溶媒分散液を得る第2工程と、この有機溶媒分散液を更に硬化性樹脂(D)と混合した後、前記有機溶媒を留去する第3工程とを含む製造方法により調製されることが好ましい。
第1工程は、20℃における水に対する溶解度が好ましくは5質量%以上で、40質量%以下(より好ましくは30質量%以下)の有機溶媒と、水性ラテックスとを混合する操作を含む。かかる有機溶媒を用いることによって、上記混合操作の後、更に水を添加すると(後述する)相分離することとなって、再分散が可能な程度の緩やかな状態の靱性改質剤緩凝集体を得ることができる。
第2工程は、緩凝集した靱性改質剤を液相から分離・回収して、靱性改質剤ドープを得る操作を含む。かかる操作によって、靱性改質剤から乳化剤等の水溶性の夾雑物を分離・除去することができる。
第3工程は、第2工程で得た靱性改質剤の有機溶媒溶液(有機溶媒分散液)中の有機溶媒を前記硬化性樹脂に置換する操作を含む。かかる操作によって、靱性改質剤が一次粒子の状態で分散した靱性改質剤分散組成物を得ることができる。また、靱性改質剤の凝集体に残存する水分を共沸留去することができる。
本発明の硬化性樹脂組成物には、必要に応じて有機過酸化物や、硬化促進剤、連鎖移動剤、光増感剤、還元剤、可塑剤、充填剤、接着性付与剤(プライマーを含む)、染料、顔料、安定剤、紫外線吸収剤、希釈剤(反応性/非反応性)、有機溶剤などを混合することができる。
本発明の硬化物は、本発明の硬化性樹脂組成物を硬化してなるものである。
硬化性樹脂組成物を硬化する方法は、硬化性樹脂(D)の種類に応じて適宜選択すればよい。
本発明の硬化性樹脂組成物は、硬化性樹脂組成物を硬化してなる硬化物において、マトリクス(樹脂)中に靱性改質剤が一次粒子分散しているものであることが好ましい。本明細書において、靱性改質剤が「一次粒子分散している」とは、靱性改質剤粒子同士が、マトリクス中で互いに凝集せず、それぞれ独立して分散していることを意味し、具体的には、粒子分散率が、50%以上であることを意味する。粒子分散率(%)は、後述の方法で以下の数式1を用いて算出する。粒子分散率は、前記靱性向上の観点から、70%以上であることが好ましく、75%以上であることがより好ましく、90%以上であることが更に好ましい。
本発明の硬化性樹脂組成物は、成形材料、接着剤、繊維あるいはフィラー強化複合材料、封止材料、注型材料、絶縁材料、コーティング材料、充填材、光造型材料、光学部品、インキ、トナーとして好適に使用される。
成形方法としては、例えば、トランスファー成形法、注型成形法、塗布焼付法、回転成形法、光造型法、更には炭素繊維、ガラス繊維等と複合させたハンドレイアップ成形法、プリプレグ成形法、引き抜き成形法、フィラメントワインディング成形法、プレス成形法、レジントランスファモールディング(RTM、VaRTM)成形法、SMC成形法などが適応できるが、これらに限定されるものではない。
[靱性改質剤の硬化性樹脂分散体A1-1]
靱性改質剤の硬化性樹脂分散体A1-1として、製造例6で合成したものを用いた。
[靱性改質剤の硬化性樹脂分散体A1-2]
靱性改質剤の硬化性樹脂分散体A1-2として、製造例6で合成したものを用いた。
[靱性改質剤の硬化性樹脂分散体A2-1]
靱性改質剤の硬化性樹脂分散体A2-1として、製造例7で合成したものを用いた。
[靱性改質剤の硬化性樹脂分散体A2-2]
靱性改質剤の硬化性樹脂分散体A2-2として、製造例7で合成したものを用いた。
[靱性改質剤の硬化性樹脂分散体A3-1]
靱性改質剤の硬化性樹脂分散体A3-1として、製造例6で合成したものを用いた。
[靱性改質剤の硬化性樹脂分散体A3-2]
靱性改質剤の硬化性樹脂分散体A3-2として、製造例6で合成したものを用いた。
[靱性改質剤の硬化性樹脂分散体A4-1]
靱性改質剤の硬化性樹脂分散体A4-1として、製造例7で合成したものを用いた。
[靱性改質剤の硬化性樹脂分散体A4-2]
靱性改質剤の硬化性樹脂分散体A4-2として、製造例7で合成したものを用いた。
[硬化性樹脂B1]
硬化性樹脂B1として、N,N,N’,N’-テトラグリシジルジアミノジフェニルメタン(ハンツマン・ジャパン株式会社製、製品名:ARALDITE MY 721 CH)を使用した。
[硬化性樹脂B2]
硬化性樹脂B2として、ビスフェノールA型液状エポキシ樹脂(三菱化学株式会社製、製品名:jER 828EL)を使用した。
[硬化剤C1]
硬化剤C1として、変性芳香族アミン(三菱化学株式会社製、製品名:jERキュア W)を使用した。
[硬化剤C2]
硬化剤C2として、4,4-ジアミノジフェニルスルホン(ハンツマン・ジャパン株式会社製、製品名:Aradur 9446-1)を使用した。
[熱可塑性樹脂D1]
熱可塑性樹脂D1として、ポリエーテルスルホン樹脂(住友化学株式会社製、スミカエクセルPES 5003P)を使用した。
[ノニオン系反応性界面活性剤E1]
ノニオン系反応性界面活性剤E1として、ポリオキシアルキレンアルケニルエーテル(花王株式会社製、ラテムルPD450)を使用した。
本実施例、製造例における評価方法は以下の通りである。
後述する曲げ弾性率測定で用いた試験片の液体窒素中での凍結破断面を、走査型電子顕微鏡(日本電子株式会社製、JSM-6300F)を用いて倍率2万倍にて観察を行い、以下の方法による粒子分散率(%)を指標として分散状態を判定した。
良好:粒子分散率が70%以上である。
不良:粒子分散率が70%未満である。
得られた2万倍の走査型電子顕微鏡写真において、5cm四方のエリアを無作為に4カ所選択して、上述の方法で粒子分散率(%)を算出し、その平均値を用いた。
体積平均粒子径は、粒子径測定装置(日機装(株)製Microtrac UPA)で測定した。
硬化板サンプルを、長さ100mm、幅(b)10mm、厚さ(h)5mmのサイズの試験片に切削後、23℃で養生、その後、オートグラフAG-2000E((株)島津製作所製)を用いて、支点間距離(L)80mm、テストスピード2mm/分の条件にて3点曲げ試験を実施した。得られた荷重(F)-たわみ(e)曲線の初期傾き(F/e)を求め、曲げ弾性率(E)を下記の数式2より算出した。ここで、(F/e)はkN/mm単位、L、b、hはmm単位である。
硬化板サンプルを長さ2.5インチ、幅(b)0.5インチ、厚さ(h)5mmのサイズの試験片に切削後、ノッチングマシーンによりVノッチを入れた。その後、Vノッチ先端からカミソリ刃を用いて試験片中央までクラックを入れた。試験片を23℃で養生後、オートグラフAG-2000E((株)島津製作所製)を用い、支点間距離(L)50mm、テストスピード1mm/分の条件で3点曲げ試験を行なった。曲げ試験から得られた最大強度F(kN)を用い、下記の数式3、及び数式4に従い、破壊靱性値K1c(MPa・m1/2)を算出した。ここで、aはVノッチの深さとVノッチ先端からクラック先端までの長さの和であり、L、h、a、及びbはcm単位である。
ポリブタジエンゴム状重合体ラテックス(R-1)
耐圧重合機中に、脱イオン水200質量部、リン酸三カリウム0.03質量部、リン酸二水素カリウム0.25質量部、エチレンジアミン四酢酸二ナトリウム(EDTA)0.002質量部、硫酸第一鉄・7水和塩(Fe)0.001質量部およびドデシルベンゼンスルホン酸ナトリウム(SDS)1.5質量部を投入し、撹拌しつつ十分に窒素置換を行なって酸素を除いた後、ブタジエン(BD)100質量部を系中に投入し、45℃に昇温した。パラメンタンハイドロパーオキサイド(PHP)0.015質量部、続いてナトリウムホルムアルデヒドスルホキシレート(SFS)0.04質量部を投入し重合を開始した。重合開始から4時間目に、PHP0.01質量部、EDTA0.0015質量部およびFe0.001質量部を投入した。重合10時間目に減圧下残存モノマーを脱揮除去して重合を終了し、ポリブタジエンゴム粒子を含むラテックス(R-1)を得た。得られたラテックスに含まれるポリブタジエンゴム粒子の体積平均粒子径は0.08μmであった。
靱性改質剤の重合(L-1)
温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、上記ポリブタジエンゴム状重合体ラテックス(R-1)210質量部(ゴム重合体成分70質量部を含む)、及び脱イオン水230質量部を仕込み、窒素置換を行いながら60℃で撹拌した。EDTA0.004質量部、硫酸第一鉄・7水和塩0.001質量部、及びSFS0.2質量部を加えた後、ノニオン系反応性界面活性剤(E1)9質量部を加え30分撹拌後、スチレン(St)14質量部、アクリロニトリル(AN)9質量部、メチルメタクリレート(MMA)4質量部、グリシジルメタクリレート(GMA)3質量部、及びクメンハイドロパーオキサイド(CHP)0.08質量部の混合物を200分間かけて連続的に添加した。添加終了後、CHP0.04質量部を添加し、更に1時間撹拌を続けて重合を完結させ、靱性改質剤を含む水性ラテックス(L-1)を得た。モノマー成分の重合転化率は99%以上であった。得られた水性ラテックスに含まれる靱性改質剤の体積平均粒子径は0.12μmであった。
靱性改質剤の重合(L-2)
ノニオン系反応性界面活性剤(E1)を添加しないこと以外は製造例2と同様の重合を実施し、靱性改質剤を含む水性ラテックス(L-2)を得た。モノマー成分の重合転化率は99%以上であった。得られた水性ラテックスに含まれるポリマー微粒子の体積平均粒子径は0.11μmであった。
三層構造を有する靱性改質剤の重合(L-3)
温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、上記ポリブタジエンゴム状重合体ラテックス(R-1)180質量部(ゴム重合体成分60質量部を含む)、及び脱イオン水230質量部を仕込み、窒素置換を行いながら60℃で撹拌した。EDTA0.004質量部、硫酸第一鉄・7水和塩0.001質量部、及びSFS0.2質量部を加えた後、St23質量部、アリルメタクリレート1.15質量部を160分間かけて連続的に添加し、更に1時間撹拌を続けた。次に、ノニオン系反応性界面活性剤(E1)5質量部を加え30分撹拌後、St7質量部、AN5質量部、MMA2質量部、GMA3質量部、及びCHP0.08質量部の混合物を200分間かけて連続的に添加した。添加終了後、CHP0.04質量部を添加し、更に1時間撹拌を続けて重合を完結させ、靱性改質剤を含む水性ラテックス(L-3)を得た。モノマー成分の重合転化率は99%以上であった。得られた水性ラテックスに含まれる靱性改質剤の体積平均粒子径は0.10μmであった。
三層構造を有する靱性改質剤の重合(L-4)
ノニオン系反応性界面活性剤(E1)を添加しないこと以外は製造例4と同様の重合を実施し、靱性改質剤を含む水性ラテックス(L-4)を得た。モノマー成分の重合転化率は99%以上であった。得られた水性ラテックスに含まれるポリマー微粒子の体積平均粒子径は0.09μmであった。
靱性改質剤の硬化性樹脂分散体A1-1、A1-2、A3-1、A3-2の製造
30℃の1L混合槽にイソブタノール126質量部を導入し、撹拌しながら、製造例2で得られた靱性改質剤の水性ラテックス(L-1)を126質量部投入した。均一に混合後、水650質量部を80質量部/分の供給速度で投入した。供給終了後、速やかに撹拌を停止したところ、浮上性の凝集体を含むスラリー液を得た。次に、凝集体を残し、液相710質量部を槽下部の払い出し口より排出させた。得られた凝集体にメチルエチルケトン(MEK)400質量部を追加して混合し、靱性改質剤が分散した有機溶媒分散液を得た。この有機溶媒分散液に硬化性樹脂(B1)を靱性改質剤/硬化性樹脂が25/75となるように添加、混合後、有機溶媒を減圧留去し、靱性改質剤を分散させた硬化性樹脂(B1)分散体A1-1として得た。また、同様に硬化性樹脂(B2)を用いることで、靱性改質剤を分散させた硬化性樹脂(B2)分散体A1-2を得た。
靱性改質剤の硬化性樹脂分散体A2-1、A2-2、A4-1、A4-2の製造
30℃の1L混合槽にMEK126質量部を導入し、撹拌しながら、製造例3で得られた靱性改質剤の水性ラテックス(L-2)を126質量部投入した。均一に混合後、水200質量部を80質量部/分の供給速度で投入した。供給終了後、速やかに撹拌を停止したところ、浮上性の凝集体を含むスラリー液を得た。次に、凝集体を残し、液相350質量部を槽下部の払い出し口より排出させた。得られた凝集体にMEK150質量部を追加して混合し、靱性改質剤が分散した有機溶媒分散液を得た。この有機溶媒分散液に硬化性樹脂(B1)を靱性改質剤/硬化性樹脂が25/75となるように添加、混合後、有機溶媒を減圧留去し、靱性改質剤を分散させた硬化性樹脂(B1)分散体A2-1として得た。また、同様に硬化性樹脂(B2)を用いることで、靱性改質剤を分散させた硬化性樹脂(B2)分散体A2-2を得た。
また、製造例5で得られた靱性改質剤の水性ラテックス(L-4)を用いることで、靱性改質剤を分散させた硬化性樹脂(B1)分散体A4-1および硬化性樹脂(B2)分散体A4-2を得た。
表2、3に示す配合率にて、硬化性樹脂と熱可塑性樹脂を撹拌しながら120℃に加温し、均一混合させた。本均一混合物に、靱性改質剤の硬化性樹脂分散体、および硬化剤を表2、3に記載の配合率で添加後、よく混合し、更に、脱泡して、硬化性樹脂組成物を得た。この硬化性樹脂組成物を、厚み5mmのスペーサーを挟んだ2枚のガラス板の間に注ぎ込み、熱風オーブン中100℃で2時間、続いて175℃で4時間硬化させ、厚み5mmの硬化板を得た。それぞれの硬化板の粒子分散状態、曲げ弾性率、K1cの結果を表2、3に示す。
表2、3に示す配合率にて、硬化性樹脂と熱可塑性樹脂を撹拌しながら120℃に加温し、均一混合させた。本均一混合物に、靱性改質剤の硬化性樹脂分散体、および硬化剤を表2、3に記載の配合率で添加後、よく混合し、更に、脱泡して、硬化性樹脂組成物を得た。この硬化性樹脂組成物を、厚み5mmのスペーサーを挟んだ2枚のガラス板の間に注ぎ込み、熱風オーブン中150℃で1時間、続いて180℃で2時間硬化させ、厚み5mmの硬化板を得た。それぞれの硬化板の粒子分散状態、曲げ弾性率、K1cの結果を表2、3に示す。
Claims (12)
- ゴム状重合体(A)ラテックス50~95質量%(ゴム重合体成分として)存在下、ビニル単量体(B)5~50質量%を、ノニオン系反応性界面活性剤(C)0.5~15質量部((A)および(B)100質量部に対し)を用いて乳化重合して得られる、硬化性樹脂(D)用靭性改質剤。
- ゴム状重合体(A)が、ジエン系単量体および(メタ)アクリル酸エステル単量体から選ばれる1種以上の単量体50~100質量%、ならびに、他の共重合可能なビニル単量体0~50質量%から構成されるゴム弾性体、ポリシロキサンゴム系弾性体、または、それらの混合物からなり、
ビニル単量体(B)が、(メタ)アクリル酸エステル単量体、芳香族ビニル単量体、シアン化ビニル単量体、不飽和酸誘導体、(メタ)アクリル酸アミド誘導体、および、マレイミド誘導体からなる群から選ばれる1種以上からなる、請求項1に記載の硬化性樹脂(D)用靭性改質剤。 - ノニオン系反応性界面活性剤(C)がポリオキシアルキレンアルケニルエーテルであることを特徴とする請求項1または2に記載の硬化性樹脂(D)用靭性改質剤。
- 三層構造を有し、ゴム状重合体(A)ラテックス存在下、ビニル単量体(B1)、および1分子中にラジカル重合性基を2以上有する単量体(E)を重合することで中間被覆層を形成し、更にビニル単量体(B2)を、ノニオン系反応性界面活性剤(C)を用いて乳化重合して得られることを特徴とする、請求項1~4のいずれかに記載の硬化性樹脂(D)用靭性改質剤。
- ゴム状重合体(A)ラテックス50~95質量%(ゴム重合体成分として)存在下、ビニル単量体(B)5~50質量%を、ノニオン系反応性界面活性剤(C)0.5~15質量部((A)および(B)の合計100質量部に対し)を用いて乳化重合する工程を含む、硬化性樹脂(D)用靭性改質剤の製造方法。
- 硬化性樹脂(D)20~99.5質量%、および、請求項1~5のいずれかに記載の靭性改質剤0.5~80質量%を含有する硬化性樹脂組成物。
- 請求項1~5のいずれかに記載の靭性改質剤を含有する水性ラテックスを、20℃における水に対する溶解度が5~40質量%以下の有機溶媒と混合した後、更に過剰の水と混合して、前記靱性改質剤を緩凝集させる第1工程と、
緩凝集した前記靱性改質剤を液相から分離して回収した後、再度有機溶媒と混合して、前記靱性改質剤の有機溶媒分散液を得る第2工程と、
前記有機溶媒分散液を更に前記硬化性樹脂(D)と混合した後、前記有機溶媒を留去する第3工程と、を含む製造方法により調製される請求項7に記載の硬化性樹脂組成物。 - 更に熱可塑性樹脂(F)を含有することを特徴とする請求項7または8に記載の硬化性樹脂組成物。
- 前記熱可塑性樹脂(F)が、ポリエーテルスルホン、ポリエーテルイミド、フェノキシ樹脂、および、ノボラック樹脂からなる群から選ばれる1種以上であることを特徴とする請求項9に記載の硬化性樹脂組成物。
- 硬化性樹脂組成物を硬化してなる硬化物において、靭性改質剤が、マトリクス中に一次粒子分散していることを特徴とする請求項7~10のいずれかに記載の硬化性樹脂組成物。
- 請求項7~11のいずれかに記載の硬化性樹脂組成物を硬化してなる硬化物。
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CA2862782A CA2862782A1 (en) | 2012-02-07 | 2013-02-05 | Toughness modifier for curable resin, and curable resin composition |
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US14/375,662 US9701822B2 (en) | 2012-02-07 | 2013-02-05 | Toughness modifier for curable resin, and curable resin composition |
EP13746769.2A EP2813525B1 (en) | 2012-02-07 | 2013-02-05 | Toughness modifier for curable resin, and curable resin composition |
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JP2016199673A (ja) * | 2015-04-09 | 2016-12-01 | 株式会社カネカ | 接着性の改善されたポリマー微粒子含有硬化性樹脂組成物 |
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KR20140129014A (ko) | 2014-11-06 |
TW201336869A (zh) | 2013-09-16 |
US20140371350A1 (en) | 2014-12-18 |
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