JP2010270328A - Polymer particle-containing dispersion and method for producing polymer particle-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer particle-containing dispersion wherein polymer particles with a high rubber content can be easily dispersed in an epoxy resin composition, for using the dispersion in production of resin cured products with low elastic moduli. <P>SOLUTION: In the method, the polymer particle-containing dispersion composed of polymer particles (A)-containing latex and organic mediums (B) and (C) is produced by mixing the predetermined organic mediums (B) and (C) with the polymer particle (A)-containing latex, and removing a water layer originated from the polymer particle (A)-containing latex. The polymer particles (A) are obtained by polymerizing 0-20 mass% of one or more kinds of monomers (b) selected from (meth)acrylates, aromatic vinyl monomers, and vinyl cyanide monomers, of which homopolymer has a glass transition temperature of 0°C or higher, in the presence of 80-100 mass% of rubber particles (a). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention mainly relates to a method for producing a polymer particle-containing dispersion by replacing a solvent with an organic solvent without recovering polymer particles from an aqueous latex.

  Generally, a cured product of a polymerizable organic compound having a reactive group, for example, a cured product of an epoxy resin, has many dimensional stability, mechanical strength, electrical insulating properties, heat resistance, water resistance, chemical resistance, and the like. Excellent in terms. However, cured products of epoxy resins have low fracture toughness and may exhibit very brittle properties, and such properties are often a problem in a wide range of applications.

  As one of the methods for solving these problems, an attempt has been made to blend a rubber component in an epoxy resin. For example, Patent Document 1 discloses a method (1) of adding reactive liquid rubber (CTBN or the like) or nitrile rubber.

  However, in the above method (1), since the reactive liquid rubber is once dissolved in the epoxy resin and then undergoes a phase separation at the time of curing, the curing obtained by the type of epoxy resin to be blended and the difference in curing conditions. There is a problem that the morphology of the product changes and the desired stress reduction effect cannot be obtained.

  Therefore, various methods (2) for recovering a rubber-like polymer prepared in advance using a polymerization method in an aqueous medium typified by emulsion polymerization, dispersion polymerization, and suspension polymerization, and adding it to an epoxy resin. (See Patent Document 2).

  However, in the method of collecting and mixing the particles once as in the method (2), for example, the coagulation method is a method of obtaining an aggregate by using a coagulant centering on an inorganic electrolyte. ) Is difficult to disperse in an epoxy resin. Furthermore, as in Patent Document 3, particles recovered by spray drying can be dispersed as primary particles, but there is a problem that fresh substances such as emulsifiers remain as impurities. Therefore, for example, in Patent Document 4, without recovering rubber-like polymer particles, the rubber-like polymer particles are directly converted into an organic solvent from an aqueous medium containing them, and after mixing with an epoxy resin, volatile components are distilled off. A method (3) for obtaining an epoxy resin composition containing rubbery polymer particles is disclosed.

  In the method (3), since it is not necessary to recover the rubbery polymer particles, it can be efficiently dispersed in the epoxy resin, and a composition with reduced impurities can be provided by introducing a washing step. . However, the rubber-like polymer particles used in this document have a low rubber content, and no mention is made of particle design of the rubber-like polymer. Therefore, in order to reduce the elastic modulus of the obtained cured product, it is necessary to increase the number of added parts, which causes problems such as an increase in the viscosity of the mixture, which is not preferable in terms of workability.

JP 57-49646 A JP-A-5-295237 International Publication No. 2005/078013 Pamphlet International Publication No. 2004/108825 Pamphlet

  Accordingly, the present invention includes polymer particles that can easily disperse polymer particles having a high rubber content in an epoxy resin composition and that can be used to produce a cured resin having a low elastic modulus. It is to provide a method for producing a dispersion.

  In the present invention, the organic medium (B) is mixed with the latex containing the polymer particles (A), the organic medium (C) having a lower solubility in water than the organic medium (B) is further mixed, and the polymer particles ( A) A method for producing a dispersion containing polymer particles (A) comprising the polymer particles (A), the organic medium (B) and the organic medium (C) by removing the aqueous layer derived from the containing latex. In the presence of 80% by mass or more and 100% by mass or less of rubber particles (a), the polymer particles (A) are (meth) acrylates or aromatic vinyls having a glass transition temperature of 0 ° C. or higher. Polymerize one or more monomers selected from monomers and vinyl cyanide monomers (b) 0% by mass to 20% by mass (provided that (a) + (b) is 100% by mass) Polymer particle (A) -containing dispersion which is a polymer particle obtained by It is a manufacturing method.

  Moreover, this invention removes the volatile component containing the said organic medium (B) and (C), after mixing the polymer particle (A) containing dispersion obtained by the said manufacturing method with a polymeric organic compound. It is a manufacturing method of the polymer particle (A) containing resin composition to do. The polymerizable organic compound is preferably an epoxy resin.

  Moreover, this invention is a hardened | cured material obtained by hardening | curing the polymer particle (A) containing resin composition obtained by the said manufacturing method.

  By using the production method of the present invention, polymer particles having a high rubber content can be efficiently dispersed in a polymerizable organic compound without being recovered as a powder. Furthermore, even if the addition amount of polymer particles is small, the elastic modulus of the resulting polymer particle (A) -containing resin cured product can be reduced.

  In the present invention, the polymer particle (A) -containing latex and the organic medium (B) are mixed, and further, the organic medium (C) having a lower solubility in water than the organic medium (B) is mixed. (A) The aqueous layer derived from the containing latex is removed. After mixing the organic medium (B), an appropriate amount of water may be added if necessary.

  The organic medium (B) used in the present invention is an organic medium partially soluble in water, and is one or more organic solvents or a mixture thereof. Preferably, it is an organic solvent having a solubility in water at 25 ° C. of 9 to 40% by mass, more preferably 10 to 30% by mass, or a mixture thereof.

  Examples of the organic medium (B) include ketones such as methyl ethyl ketone, acetone, diethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ethanol, (iso) propanol, butanol, and the like Alcohols such as tetrahydrofuran, tetrahydropyran, dioxane and diethyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; one or more organic compounds selected from halogenated hydrocarbons such as methylene chloride and chloroform A solvent or a mixture thereof may be mentioned.

  The amount of the organic medium (B) can vary depending on the type of the polymer particles (A) and the amount of the polymer particles (A) contained in the aqueous latex of the polymer particles (A). 50-350 mass parts is preferable with respect to 100 mass parts of latex of (A), and 50-200 mass parts is more preferable.

  The organic medium (C) used in the present invention is an organic medium having a lower solubility in water than the organic medium (B), and is one or more organic solvents or a mixture thereof. Preferably, an organic solvent or a mixture thereof having a solubility in water at 25 ° C. of 8% by mass or less, more preferably 6% by mass or less, and still more preferably 4% by mass or less. When the solubility of the organic medium (C) in water is in the above range, the effect of promoting the separation of the organic layer and the aqueous layer is likely to be sufficient.

  Examples of the organic medium (C) include ketones such as diethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; ethers such as diethyl ether and butyl ether; benzene, toluene, xylene and the like Aromatic hydrocarbons; Aliphatic hydrocarbons such as hexane; One or more organic solvents selected from halogenated hydrocarbons such as methylene chloride and chloroform, or a mixture thereof.

  The organic medium (C) can be used in an amount having an effect of promoting the separation of the organic medium layer and the aqueous layer, and is preferably used 1.5 times or more than the organic medium (B) to be used.

  Examples of the combination of the organic medium (B) and the organic medium (C) used in the present invention include a combination of methyl ethyl ketone and methyl isobutyl ketone.

  For the purpose of completely removing impurities, after mixing with the organic media (B) and (C), the aqueous layer is removed, and then the same operation can be repeated.

  The polymer particles (A) of the present invention comprise a (meth) acrylate, an aromatic vinyl monomer and a vinyl cyanide monomer having a glass transition temperature of 0 ° C. or higher in the presence of rubber particles (a). Polymer particles obtained by polymerizing one or more monomers (b) selected from monomers, wherein (a) is 80% by mass or more and 100% by mass or less, and (b) is 0% by mass or more. 20% by mass or less (provided that (a) + (b) is 100% by mass). Here, it is preferable that (a) is 96 mass% or more and 99 mass% or less, and (b) is 1 mass% or more and 4 mass% or less.

  In addition, (meth) acrylate refers to acrylate or methacrylate.

  If the rubber particles (a) used in the polymerization of the polymer particles (A) are 80% by mass or more, the number of parts to be added for reducing the elastic modulus of the resulting cured product can be suppressed. ) Since the viscosity of the contained resin composition does not increase, the handleability is good.

  For example, in WO 2004/108825 pamphlet, the same operation as the present invention is performed, but the rubber content of the polymer particles listed in the examples is 70% by mass. In order to reduce the elastic modulus of the cured epoxy resin, it is necessary to add a large amount of polymer particles.

  When the rubber particles (a) used during the polymerization of the polymer particles (A) are in the range of 80% by mass to 95% by mass, the polymer particles (A) can be recovered by spray drying. It is possible to produce a dispersion containing polymer particles (A) by re-dispersing the polymer. However, by using the production method of the present invention, the step of recovering the polymer particles (A) as powder can be omitted, and the working efficiency can be increased.

  If the rubber particles (a) used in the polymerization of the polymer particles (A) are 96% by mass or more, there are few graft parts, so that recovery by spray drying becomes difficult. Therefore, a dispersion in a solvent can be obtained only by the production method of the present invention, which is optimal.

  In particular, if (a) is 96% by mass or more, it is effective in reducing the elastic modulus of the resulting cured product, and if (a) is 99% by mass or less, the polymer particles ( A) Dispersibility as primary particles becomes better.

  That is, the present invention efficiently separates water from the polymer particles (A) without taking out the polymer particles (A) obtained in the form of an aqueous latex as a powder, and then a polymerizable organic compound such as an epoxy resin. The polymer particles (A) can be uniformly mixed and dispersed in a polymerizable organic compound such as an epoxy resin by mixing with the same, and at the same time, impurities such as emulsifiers added during the polymerization of the polymer particles (A) can be removed. Is an efficient way to implement. Furthermore, the polymer particles (A) -containing resin composition in which the polymer particles are easily and uniformly dispersed by mixing the polymer particles (A) having a high rubber content with a polymerizable organic compound such as an epoxy resin. Can be obtained.

  The polymer particles (A) can be produced, for example, by emulsion polymerization or soap-free emulsion polymerization.

  Examples of the polymerization initiator used for emulsion polymerization include azo compounds such as 2,2′-azobisisobutyronitrile and 4,4′-azobis- (4-cyanovaleric acid); ammonium persulfate salts, and the like. Persulfuric acid compounds; organic peroxides such as diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; redox initiators comprising the persulfuric acid compound as one component; Redox initiators containing the above organic peroxide as one component may be mentioned.

  Among these, ammonium persulfate and 4,4′-azobis- (4-cyanovaleric acid) are preferably used because the content of metal ions as impurities can be reduced. Also, other polymerization initiators can be used in combination as long as they do not depart from the object of the present invention.

  The polymerization temperature can be appropriately carried out in the range of about 40 to 80 ° C.

  A known emulsifier can be used as the emulsifier used in the emulsion polymerization. This may be an anionic emulsifier, a cationic emulsifier, or a nonionic emulsifier, but it is preferable to use an ammonium salt type anionic emulsifier or a nonionic emulsifier because the content of metal ions as impurities can be reduced.

  Examples of ammonium salt type anionic emulsifiers include ammonium lauryl sulfate, ammonium alkylsulfosuccinate, and alkenylsulfosuccinic acid. From the viewpoint of the stability of the emulsifier, ammonium lauryl sulfate and ammonium di-2-ethylhexylsulfosuccinate are preferred.

  Examples of nonionic emulsifiers include polyoxyethylene monotetradecyl ether.

  Further, other emulsifiers can be used in combination as long as they do not depart from the object of the present invention.

  It is preferable to use a small amount of the emulsifier in the production process of the polymer particle (A) latex within a range that does not hinder the emulsion stability. Or it is preferable to have the property of being extracted and washed in the aqueous layer up to a residual amount that does not affect the physical properties of the epoxy resin composition to be produced in the steps of carrying out the production method of the present invention.

  The rubber particles (a) are those having a glass transition temperature of less than 0 ° C., and diene rubber, acrylic rubber, silicone rubber, or silicone / acrylic composite rubber can be used.

  The diene rubber is obtained by polymerizing 1,3-butadiene or 1,3-butadiene and a vinyl monomer, and has a crosslinked structure.

  Examples of vinyl monomers include aromatic vinyl monomers such as styrene and α-methylstyrene; alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate; acrylonitrile and methacrylonitrile. Vinyl cyanide monomers; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride and vinylidene bromide; glycidyl (meth) acrylate and allyl glycidyl ether And vinyl monomers having a glycidyl group. These can be used alone or in combination of two or more.

  Moreover, in order to adjust molecular weight and a crosslinking degree, a crosslinkable monomer can also be used together.

  Examples of the crosslinkable monomer include polyfunctional aromatic vinyl monomers such as divinylbenzene; dihydric alcohols such as ethylene glycol di (meth) acrylate and 1,3-butylene glycol di (meth) acrylate; Examples include tri (meth) acrylates; allyl (meth) acrylates; di- or triallyl compounds such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate. These can be used alone or in combination of two or more.

  Here, allyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, and triallyl isocyanurate also have a role as a graft crossing agent.

  The crosslinkable monomer is preferably used in the range of 20 parts by mass or less, and in the range of 0.1 to 18 parts by mass with respect to the total (100 parts by mass) of 1,3-butadiene and the vinyl monomer. More preferably, it is used.

  The acrylic rubber is obtained by polymerizing alkyl (meth) acrylate or alkyl (meth) acrylate and another vinyl monomer, and has a crosslinked structure.

  Examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethoxyethoxyethyl acrylate, and methoxytripropylene glycol. Examples include acrylate, 4-hydroxybutyl acrylate, dodecyl methacrylate, and stearyl methacrylate. These can be used alone or in combination of two or more.

  Examples of other vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyl toluene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; methacrylic acid-modified silicone, fluorine-containing Various vinyl monomers such as vinyl monomers can be mentioned. These can be used alone or in combination of two or more.

  Moreover, in order to adjust molecular weight and a crosslinking degree, a crosslinkable monomer can also be used together.

  Examples of the crosslinkable monomer include polyfunctional aromatic vinyl monomers such as divinylbenzene; dihydric alcohols such as ethylene glycol di (meth) acrylate and 1,3-butylene glycol di (meth) acrylate; Examples include tri (meth) acrylates; allyl (meth) acrylates; di- or triallyl compounds such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate. These can be used alone or in combination of two or more.

  Here, allyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, and triallyl isocyanurate also have a role as a graft crossing agent.

  The crosslinkable monomer is preferably used in a range of 20 parts by mass or less with respect to the total (100 parts by mass) of the alkyl (meth) acrylate and other vinyl monomers, and is 0.1 to 18 parts by mass. It is more preferable to use within a range.

  The acrylic rubber may have a single layer or a multilayer structure of two or more stages, or may be an acrylic composite rubber that includes two or more components and has two or more glass transition temperatures.

  The silicone rubber is obtained by polymerizing dimethylsiloxane, siloxane having a vinyl polymerizable functional group, and a siloxane crosslinking agent, and has a crosslinked structure.

  Examples of dimethylsiloxane include 3- or more-membered dimethylsiloxane-based rings, and those having 3 to 7 members are preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.

  A siloxane having a vinyl polymerizable functional group has a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond. As the siloxane having a vinyl polymerizable functional group, various alkoxysilane compounds having a vinyl polymerizable functional group are preferable in consideration of reactivity with dimethylsiloxane.

  Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, and methacryloyloxysilane such as γ-methacryloyloxypropyldiethoxymethylsilane or δ-methacryloyloxybutyldiethoxymethylsilane. These can be used alone or in combination of two or more.

  Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. These can be used alone or in combination of two or more.

  Silicone rubber can be obtained by using these.

  As a method for producing a silicone rubber, for example, a latex obtained by emulsifying a siloxane mixture containing a diorganosiloxane, a siloxane having a vinyl polymerizable functional group, and a siloxane crosslinker with an emulsifier and water, is subjected to shearing force by high-speed rotation. The particles are formed using a homomixer that converts to a high-pressure generator or a homogenizer that generates particles with a jet output from a high-pressure generator, then polymerized at a high temperature using an acid catalyst, and then neutralized with an alkaline substance. be able to.

  Examples of the method for adding an acid catalyst include a method of mixing with a siloxane mixture, an emulsifier and water, and a method of dropping a latex in which a siloxane mixture is granulated into a hot acid aqueous solution at a constant rate. Since the control of the particle diameter is easy, a method in which the latex in which the siloxane mixture is granulated is dropped into a hot acid aqueous solution at a constant rate is preferable.

  Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid; and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These can be used alone or in combination of two or more.

  The polymerization can be stopped by cooling the reaction solution and neutralizing the acid of the silicone rubber latex with an alkaline substance such as sodium hydroxide, potassium hydroxide or sodium carbonate.

  As the silicone / acrylic composite rubber, an alkyl (meth) acrylate rubber is combined with the above silicone rubber. The silicone / acrylic composite rubber can be prepared by adding an alkyl (meth) acrylate to the latex of the silicone rubber and polymerizing it with the action of a normal radical polymerization initiator.

  As a method of adding alkyl (meth) acrylate, there are a method of batch mixing with a latex of silicone rubber and a method of dropping at a constant rate into a latex of silicone rubber.

  The polymer particles (A) are (meth) acrylate, aromatic vinyl monomer and vinyl cyanide monomer having a glass transition temperature of 0 ° C. or higher in the presence of latex of rubber particles (a). It can obtain by adding one or more types of monomers (b) chosen from these, and carrying out graft polymerization.

  Examples of the (meth) acrylate having a homopolymer glass transition temperature of 0 ° C. or higher include methyl methacrylate, ethyl methacrylate, ethyl acrylate, and glycidyl methacrylate.

  Examples of the aromatic vinyl monomer having a glass transition temperature of a homopolymer of 0 ° C. or higher include styrene, α-methylstyrene, various halogen-substituted styrenes, and alkyl-substituted styrenes.

  Examples of the vinyl cyanide monomer having a homopolymer glass transition temperature of 0 ° C. or higher include acrylonitrile and methacrylonitrile.

  As the monomer (b), a monomer other than those described above, a crosslinkable monomer, and a chain transfer agent can be used in combination as necessary.

  The monomer (b) can be graft-polymerized in multiple stages of two or more stages, if necessary, from the balance between dispersibility in the resin and stress relaxation properties.

  The average particle diameter of the polymer particles (A) is preferably from 300 nm to 10.0 μm, more preferably from 400 nm to 2.0 μm, particularly preferably from 500 nm to 1.0 μm. When the average particle diameter of the polymer particles (A) is 300 nm or more, the dispersibility in the resin composition is excellent. Moreover, if the average particle diameter of a polymer particle (A) is 10.0 micrometers or less, the characteristic which an epoxy resin hardened | cured material has can be preferably maintained.

  The average particle diameter of the polymer particles (A) can be measured by a laser diffraction scattering method using the latex of the polymer particles (A). In addition, the average particle diameter described in this application shows the volume average primary particle diameter (Dv) of latex.

  The polymer particle (A) -containing dispersion of the present invention preferably has a moisture content of 0.2% by mass or less, and more preferably 0.1% by mass or less.

  Moreover, this invention removes the volatile component containing the said organic medium (B) and (C), after mixing the polymer particle (A) containing dispersion obtained as mentioned above, and a polymerizable organic compound. By this, it is related with the method of manufacturing a polymer particle (A) containing resin composition.

  The polymerizable organic compound is preferably an epoxy resin, for example.

  The volatile component contained in the polymer particle (A) -containing resin composition is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less.

  The epoxy resin is not particularly limited in molecular structure, molecular weight, etc. as long as it has at least two epoxy bonds in the molecule. For example, various epoxy resins such as dicyclopentadiene type, cresol novolak type, phenol novolak type, bisphenol type, and biphenyl type can be used alone or in combination of two or more.

  Examples of the curing agent used for curing the epoxy resin include a phenolic curing agent such as a phenol novolac resin and a cresol novolac resin, an amine curing agent, and an acid anhydride curing agent. These can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular about the usage-amount, it is necessary to add the stoichiometric amount of hardening of an epoxy group.

  Various known phenolic curing agents can be used. Examples thereof include resol type or novolac type phenolic curing agents derived from various phenols and formaldehyde or C2 or higher aldehydes. These phenolic curing agents may be modified with drying oil, xylene resin, melamine resin or the like. In the case of a novolac type phenolic curing agent, a curing agent such as a polyamine such as hexamine, an epoxy resin, an isocyanate compound, a polyformaldehyde compound, or a resol type phenolic resin can be further used in combination.

  In the polymer particle (A) -containing resin composition, the content of the polymer particle (A) is preferably 0.5 to 80 parts by mass, more preferably 1 to 70 parts by mass with respect to 100 parts by mass of the epoxy resin. 3-60 mass parts is still more preferable, and 3-50 mass parts is especially preferable.

  If the content of the polymer particles (A) is 0.5 parts by mass or more with respect to 100 parts by mass of the epoxy resin, the effect of reducing the elastic modulus of the cured epoxy resin is sufficiently exhibited, and 80 parts by mass or less. For example, the viscosity of the epoxy resin composition is not increased and the handleability is excellent.

  The obtained polymer particle (A) -containing resin composition (for example, an epoxy resin composition) is appropriately diluted with a polymerizable organic compound such as an epoxy resin so that the content of the desired polymer particles (A) is obtained. It can also be used as a so-called master batch. The polymerizable organic compound such as an epoxy resin used for dilution may be the same as the polymerizable organic compound such as an epoxy resin of the composition, or may be a different type as required.

  The operation of mixing the polymer particle (A) -containing dispersion with a polymerizable organic compound such as an epoxy resin can be carried out by a known method without using a special apparatus or method. For example, it can be carried out by a method and conditions used when dissolving a polymerizable organic compound such as an epoxy resin in an organic solvent. Moreover, in these series of operations, the polymer particles (A) do not cause irreversible aggregation, and the polymer particles (A) maintain a good dispersion state before and after mixing with a polymerizable organic compound such as an epoxy resin. is doing.

  In the preferable form of this invention, the polymer particle (A) is maintaining the state disperse | distributed substantially with the primary particle substantially before and after mixing to polymerizable organic compounds, such as an epoxy resin.

  Next, as a method for removing volatile components mainly composed of organic media (B) and (C) from a mixture comprising a polymer particle (A) -containing dispersion and a polymerizable organic compound such as an epoxy resin, a well-known method is known. The method is applicable. For example, a batch-type method in which the mixture is charged in a tank and heated to distill off volatile components under normal or reduced pressure, a method in which a dry gas is brought into contact with the mixture in the tank, a continuous type using a thin film evaporator And a method using an extruder equipped with a devolatilizer or a continuous stirring tank.

  Conditions such as temperature and required time for removing the volatile component can be appropriately selected within a range in which a polymerizable organic compound such as an epoxy resin reacts or quality is not impaired.

  Depending on the final use form of the polymer particle (A) -containing resin composition such as an epoxy resin composition, the organic medium (B) and (C) may be used without being removed. Similarly, in such a case, the polymer particles are not agglomerated and are well dispersed in a solution in which a polymerizable organic compound such as an epoxy resin is dissolved in the mixed organic medium of the remaining organic medium (B) and (C). Can be obtained.

  The amount of the organic medium (B) and (C) remaining in the epoxy resin composition is within a range in which there is no problem depending on the purpose of use of the polymer particle (A) -containing resin composition such as the epoxy resin composition. It can be selected as appropriate.

  Furthermore, as another feature of the present invention, there is a possibility that a harmful effect may be exerted when using a polymerizable organic compound such as an epoxy resin such as an emulsifier ordinarily used in the production of an aqueous latex of the polymer particles (A). Certain impurities can be easily removed. Further, if a high-purity latex of polymer particles with few impurities in advance and the amount of residual ions is suppressed is used, the residue can be sufficiently removed simply by contacting with an organic medium.

  The temperature at which the organic medium (B) is mixed with the polymer particles (A) varies depending on the type of the organic medium (B), so that the partial solubility in water changes and affects the separation of the organic layer and the aqueous layer. It is desirable to do. Moreover, separation of the organic layer and the aqueous layer can be brought into a preferable state by appropriately setting the temperature using such properties.

  Polymer particle (A) -containing resin composition such as an epoxy resin composition produced by the method of the present invention as described above is a paint, coating agent, aircraft part, sports equipment, fiber reinforced composite material or filler reinforced composite material. For various applications in which polymerizable organic compounds such as epoxy resins are normally used, such as structural materials such as adhesives, adhesive materials, semiconductor encapsulants or electronic materials such as electronic circuit boards, etc. By using a part or all of the polymerizable organic compound as the composition of the present invention, it can be widely used.

  In the polymer particle (A) -containing resin composition such as an epoxy resin composition, the dispersion state of the polymer particle (A) in the cured product is excellent, and there are few impurities, and even when added in a small amount, fracture toughness is achieved. An excellent cured product can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.

  The abbreviations indicate the following substances, respectively.

MEK: methyl ethyl ketone MIBK: methyl isobutylene ketone The analytical measurement methods described in the examples are described below.

[1] Average Particle Diameter of Polymer Particles (A) The average particle diameter of the polymer particles (A) is a volume as latex particle diameter using a laser diffraction scattering type particle size distribution device (LA-910W, manufactured by Horiba, Ltd.). The average primary particle diameter (Dv) was measured. The median diameter was used as the average diameter.

  The latex sample concentration of the polymer particles (A) was appropriately adjusted so as to be within an appropriate range in the scattered light intensity monitor attached to the apparatus.

[2] Spray drying of latex containing polymer particles (A) The polymer particles (A) are sprayed into a fine liquid with a pressure nozzle type using a L-8 type spray dryer manufactured by Okawara Chemical Co., Ltd. And spray dried.

<Spray drying treatment conditions>
Spray system: Rotating disk type Disk rotation speed: 25,000 rpm
Hot air temperature Inlet temperature: 145 ° C
Outlet temperature: 65 ° C
<Judgment of recoverability by spray drying>
○: Powder can be recovered without problems.

    Δ: Some blocking occurs at the nozzle, and the rotational speed of the rotating body is disturbed, but it can be recovered as powder.

    X: Blocking occurs at the nozzle and cannot be recovered as a powder.

[3] Water content Polymer particles (A) containing polymer particles (A) mixed with organic media (B) and (C), and water layers derived from the polymer particles (A) containing latex were removed (A ) The water content of the contained dispersion was quantified by the Karl Fischer method.

[4] Distillation of Volatile Components in Epoxy Resin Composition In Examples and Comparative Examples, the organic medium was distilled off under reduced pressure at 10 ⁻¹ Pa at 100 ° C. for 4 hours to obtain an epoxy resin composition.

  Then, it was dried in an oven at 180 ° C. for 20 minutes, and the decrease in mass was calculated as a volatile component.

[5] Curing of epoxy resin composition 110 g or 120 g of epoxy resin composition obtained in each of the examples and comparative examples, 85 g of MH-700 (manufactured by Nihon Riken) as a curing agent, and N- as a curing accelerator. 1.25 g of benzyl-2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed.

  The mixture was cast into a 150 mm × 150 mm × 3 mm size mold, preliminarily cured by holding in a gear oven at 80 ° C. for 2 hours, and then cured by holding at 120 ° C. for 6 hours to obtain a cured product.

[6] Elastic modulus of polymer resin (A) -containing epoxy resin cured product The obtained cured product was cut into 10 mm × 60 mm × 3 mm (JIS K-7171), and a constant temperature and humidity chamber (temperature: 23 ° C., humidity: (50%) for 24 hours or more, and then measured with an analyzer STROGRAPH-T (manufactured by Toyo Seiki Seisakusho) at a load range of 50 kgf and a test speed of 1 mm / min.

[7] Observation of dispersion state of polymer particles (A) with a transmission electron microscope A part of the obtained cured product was cut out, and the polymer particles (A) were stained with osmium tetroxide, and then sliced out and transmitted. The dispersion state of the polymer particles (A) in the cured product of the epoxy resin composition was confirmed at 5000 to 10,000 times using a scanning electron microscope (manufactured by JEOL Ltd., JEM-1200EX). When three or more particles are adjacent to each other, an aggregate is obtained.

(Production Example 1) Production Method of Latex Containing Polymer Particles (A1) In a separable flask equipped with a cooling tube, 94.77 parts of deionized water, 4.95 parts of n-butyl acrylate, and 0.05 parts of allyl methacrylate were added. I put it in. The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the temperature was raised to 80 ° C. while stirring at 250 rpm in the nitrogen atmosphere.

  Next, a pre-prepared solution of 0.10 parts of ammonium persulfate and 6.25 parts of deionized water was added all at once and held for 60 minutes to perform the first stage soap-free emulsion polymerization.

  Next, a mixed solution of 90.73 parts of n-butyl acrylate, 2.27 parts of allyl methacrylate, 0.98 parts of ammonium di-2-ethylhexyl sulfosuccinate, and 46.5 parts of deionized water was added dropwise over 294 minutes. The emulsion was polymerized in the second stage for a period of time to obtain rubber particles (a1) latex.

  The resulting rubber particle (a1) latex was mixed with 1.96 parts of methyl methacrylate, 0.04 part of n-butyl acrylate, 0.02 part of ammonium di-2-ethylhexylsulfosuccinate, and 1 part of deionized water. After dripping over 1 minute and holding for 1 hour, the emulsion polymerization was terminated to obtain a latex containing polymer particles (A1).

  The average particle diameter of the polymer particles (A1) was 638 nm. Although the obtained polymer particle (A1) -containing latex was spray-dried, it was blocked with a nozzle and could not be recovered as a powder.

(Production Example 2) Method for producing polymer particle (A2) -containing latex In the same manner as in Production Example 1, soap-free emulsion polymerization of the first stage was performed.

  Next, a mixed solution of 87.8 parts of n-butyl acrylate, 2.2 parts of allyl methacrylate, 0.95 part of ammonium di-2-ethylhexylsulfosuccinate, and 45 parts of deionized water was dropped over 285 minutes and held for 1 hour. Then, the second stage emulsion polymerization was performed to obtain rubber particles (a2) latex.

  A mixture of 4.90 parts of methyl methacrylate, 0.1 part of n-butyl acrylate, 0.05 part of ammonium di-2-ethylhexylsulfosuccinate and 3.75 parts of deionized water is added to the obtained rubber particle (a2) latex. Was added dropwise over 15 minutes and held for 1 hour, and then the emulsion polymerization was terminated to obtain a latex containing polymer particles (A2).

  The average particle diameter of the polymer particles (A2) was 668 nm. In addition, although the obtained polymer particle (A2) latex was spray-dried, it was slightly blocked by a nozzle and was difficult to recover as a powder.

Production Example 3 Production Method of Latex Containing Polymer Particles (A3) In the same manner as in Production Example 1, soap-free emulsion polymerization of the first stage was performed.

  Next, a mixed solution of 73.17 parts of n-butyl acrylate, 1.83 parts of allyl methacrylate, 0.80 parts of ammonium di-2-ethylhexyl sulfosuccinate and 37.5 parts of deionized water was added dropwise over 240 minutes. The emulsion was polymerized in the second stage for a period of time to obtain rubber particles (a3) latex.

  A mixture of 19.6 parts of methyl methacrylate, 0.40 parts of n-butyl acrylate, 0.20 parts of ammonium di-2-ethylhexyl sulfosuccinate and 10 parts of deionized water was added to the obtained rubber particle (a3) latex. After dripping over 1 minute and holding for 1 hour, the emulsion polymerization was terminated to obtain a latex containing polymer particles (A3).

  The average particle diameter of the polymer particles (A3) was 639 nm. When the obtained polymer particle (A3) -containing latex was spray-dried, there was no blocking at the nozzle and it could be recovered as a powder.

(Production Example 4) Production Method of Latex Containing Polymer Particles (A4) In the same manner as Production Example 1, soap-free emulsion polymerization of the first stage was performed.

  Next, a mixture of 91.4 parts of 2-ethylhexyl acrylate, 1.60 parts of allyl methacrylate, 0.98 parts of ammonium di-2-ethylhexyl sulfosuccinate, and 46.5 parts of deionized water was added dropwise over 294 minutes. The emulsion was polymerized in the second stage for a period of time to obtain rubber particles (a4) latex.

  To the obtained rubber particle (a4) latex, a mixed solution of 1.96 parts of methyl methacrylate, 0.04 part of n-butyl acrylate, 0.02 part of ammonium di-2-ethylhexylsulfosuccinate and 1 part of deionized water was added. After dropping over 1 minute and holding for 1 hour, the emulsion polymerization was terminated to obtain a latex containing polymer particles (A4).

  The average particle diameter of the polymer particles (A4) was 622 nm. Although the obtained polymer particle (A4) -containing latex was spray-dried, it was blocked by a nozzle and could not be recovered as a powder.

(Production Example 5) Method for producing polymer particle (A5) -containing latex In the same manner as in Production Example 1, first-stage soap-free emulsion polymerization and second-stage emulsion polymerization were performed, and rubber particles (a5) latex were obtained. Obtained.

  A mixture of 0.5 part of acrylonitrile, 1.5 parts of styrene, 0.02 part of ammonium di-2-ethylhexylsulfosuccinate, and 1 part of deionized water was added dropwise to the resulting rubber particle (a5) latex over 6 minutes. After holding for 1 hour, the emulsion polymerization was terminated to obtain a latex containing polymer particles (A5).

  The average particle diameter of the polymer particles (A5) was 645 nm. Although the obtained polymer particle (A5) -containing latex was spray-dried, it was blocked by a nozzle and could not be recovered as a powder.

(Production Example 6) Production Method of Latex Containing Polymer Particles (A6) 2.0 parts of γ-methacryloyloxypropyldimethoxymethylsilane, 2.0 parts of tetraethoxysilane and 96.0 parts of octamethylcyclotetrasiloxane were mixed. 100 parts of a siloxane-based mixture were obtained. To this was added 150 parts of deionized water in which 1.00 part of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred for 5 minutes at 10,000 rpm with a homomixer. A siloxane latex was obtained.

  The above latex was placed in a separable flask equipped with a condenser, and a mixture of 0.20 parts of sulfuric acid and 30.0 parts of deionized water was added over 3 minutes. The aqueous solution was heated at 80 ° C., maintained at the temperature for 6 hours, and cooled. Next, this reaction product was neutralized with an aqueous sodium hydroxide solution to obtain rubber particles (a6) latex.

  The obtained rubber particle (a6) latex was dried at 180 ° C. for 30 minutes to obtain a solid content of 29.42%. The rubber particles (a6) had an average particle size of 413.7 nm.

  333.11 parts of the obtained rubber particles (a6) latex (98.00 parts in terms of polymer) were put into a separable flask equipped with a cooling tube.

  The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the temperature was raised to 80 ° C. When the liquid temperature reached 80 ° C., a previously prepared solution of 0.10 parts of ammonium persulfate and 0.63 parts of deionized water was added all at once.

  Next, a mixed solution of 1.96 parts of methyl methacrylate, 0.04 part of n-butyl acrylate, 0.02 part of ammonium di-2-ethylhexylsulfosuccinate and 1 part of deionized water was dropped over 6 minutes, and held for 1 hour. The emulsion polymerization was terminated, and a polymer particle (A6) -containing latex was obtained.

  The average particle size of the polymer particles (A6) was 496 nm. The obtained polymer particle (A6) -containing latex was spray-dried, but blocked with a nozzle and could not be recovered as a powder.

Production Example 7 Production Method of Latex Containing Polymer Particles (7) In the same manner as in Production Example 1, first-stage soap-free emulsion polymerization was performed.

  Next, a mixed solution of 91.71 parts of n-butyl acrylate, 2.29 parts of allyl methacrylate, 0.99 parts of ammonium di-2-ethylhexyl sulfosuccinate and 47 parts of deionized water was added dropwise over 297 minutes and held for 1 hour. Then, the second stage emulsion polymerization was performed to obtain rubber particles (a7) latex.

  A mixture of 0.98 parts of methyl methacrylate, 0.02 parts of n-butyl acrylate, 0.01 parts of ammonium di-2-ethylhexylsulfosuccinate, and 0.5 parts of deionized water is added to the obtained rubber particles (a7) latex. Was added dropwise over 3 minutes and held for 1 hour, and then the emulsion polymerization was terminated to obtain a latex containing polymer particles (A7).

  The average particle diameter of the polymer particles (A7) was 650 nm. The obtained polymer particles (A7) latex was spray-dried, but blocked with a nozzle and could not be recovered as a powder.

(Production Example 8) Method for producing polymer particle (A8) -containing latex In the same manner as in Production Example 1, soap-free emulsion polymerization of the first stage was performed.

  Next, a mixed solution of 92.68 parts of n-butyl acrylate, 2.32 parts of allyl methacrylate, 1 part of ammonium di-2-ethylhexyl sulfosuccinate, and 71.25 parts of deionized water was added dropwise over 300 minutes and held for 1 hour. Then, the second stage emulsion polymerization was performed to obtain rubber particles (a8) latex. In Production Example 8, the rubber particles (a8) are polymer particle (A8) -containing latex.

  The average particle diameter of the polymer particles (A8) was 640 nm. Although the obtained polymer particle (A8) -containing latex was spray-dried, it was blocked with a nozzle and could not be recovered as a powder.

(Production Example 9) Method for Producing Polymer Particle (A9) -Containing Latex In the same manner as in Production Example 1, soap-free emulsion polymerization of the first stage was performed.

  Next, a mixed solution of 63.41 parts of n-butyl acrylate, 1.59 parts of allyl methacrylate, 0.7 parts of ammonium di-2-ethylhexyl sulfosuccinate, and 32.5 parts of deionized water was dropped over 210 minutes. The emulsion was subjected to emulsion polymerization at the second stage for a period of time to obtain rubber particles (a9) latex.

  To the obtained rubber particle (a9) latex, a mixed solution of 29.75 parts of methyl methacrylate, 0.25 part of n-butyl acrylate, 0.3 part of ammonium di-2-ethylhexylsulfosuccinate, and 15 parts of deionized water was added. After dripping over 1 minute and holding for 1 hour, the emulsion polymerization was terminated to obtain a latex containing polymer particles (A9).

  The average particle diameter of the polymer particles (A9) was 651 nm. When the obtained polymer particle (A9) -containing latex was spray-dried, powder could be recovered without blocking with a nozzle.

  The abbreviations listed in Table 1 indicate the following contents.

Ac system: Acrylic system Si system: Silicone system BA: n-Butyl acrylate EHA: 2-Ethylhexyl acrylate MMA: Methyl methacrylate AN: Acrylonitrile St: Styrene (Example 1) Production of dispersion 500 mL glass kept at 25 ° C In a container, 100 g of MEK (solubility in water at 25 ° C .: 11%) as an organic medium (B) component was taken, and 100 g of the polymer particle (A1) -containing latex obtained in Production Example 1 was added and stirred. After stirring 40 g of water while stirring the resulting mixture of the polymer particle (A1) -containing latex and the organic medium (B), 160 g of MIBK (solubility in water at 25 ° C .: 2%) is used as the organic medium (C). Was added.

  At this time, separation of water from the mixed organic medium layer was observed. Stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the aqueous layer was discharged to separate the polymer particle (A1) -containing dispersion. The discharged aqueous layer was about 100 g. Polymer particles (A1) were not observed in the separated aqueous layer. The obtained polymer particle (A1) -containing dispersion was subjected to dehydration treatment and filtration treatment with molecular sieve 3A manufactured by Kanto Chemical. The polymer particles (A1) -containing dispersion obtained by this operation had a water content of 0.05% and a solid content of 11.97%.

  Next, the obtained polymer particle (A1) -containing dispersion was mixed with 100 parts of an epoxy resin compound (Japan Epoxy Resin Co., Ltd., Epicoat 828) so that the polymer particles (A1) would be 10 parts. Then, the volatile component was distilled off under reduced pressure at 100 ° C. for 4 hours to obtain a polymer particle (A1) -containing epoxy resin composition. The volatile components of the resulting polymer particle (A1) -containing epoxy resin composition are shown in Table 2.

(Example 2)
The polymer particle (A1) -containing dispersion obtained was mixed with 100 parts of an epoxy resin compound (Japan Epoxy Resin Co., Ltd., Epicoat 828) so that the polymer particles (A1) were 20 parts. The same operation as in Example 1 was performed. The volatile components of the resulting polymer particle (A1) -containing epoxy resin composition are shown in Table 2.

(Example 3)
The same operation as in Example 1 was performed except that the polymer particle (A2) -containing latex obtained in Production Example 2 was used. The obtained polymer particle (A2) -containing dispersion had a water content of 0.07% and a solid content of 11.67%. The volatile components of the resulting polymer particle (A2) -containing epoxy resin composition are shown in Table 2.

Example 4
The same operation as in Example 1 was performed except that the polymer particle (A3) -containing latex obtained in Production Example 3 was used. The obtained polymer particle (A3) -containing dispersion had a water content of 0.05% and a solid content of 12.08%. The volatile components of the resulting polymer particle (A3) -containing epoxy resin composition are shown in Table 2.

(Example 5)
The same operation as in Example 1 was performed except that the polymer particle (A4) -containing latex obtained in Production Example 4 was used. The resulting polymer particle (A4) -containing dispersion had a water content of 0.07% and a solid content of 11.98%. The volatile components of the resulting polymer particle (A4) -containing epoxy resin composition are shown in Table 2.

(Example 6)
The same operation as in Example 1 was performed except that the polymer particle (A5) -containing latex obtained in Production Example 5 was used. The resulting polymer particle (A5) -containing dispersion had a water content of 0.05% and a solid content of 10.45%. The volatile components of the resulting polymer particle (A5) -containing epoxy resin composition are shown in Table 2.

(Example 7)
The same operation as in Example 1 was performed except that the polymer particle (A6) -containing latex obtained in Production Example 6 was used. The obtained polymer particle (A6) -containing dispersion had a water content of 0.06% and a solid content of 12.33%. The volatile components of the resulting polymer particle (A6) -containing epoxy resin composition are shown in Table 2.

(Example 8)
The same operation as in Example 1 was performed except that the polymer particle (A7) -containing latex obtained in Production Example 7 was used. The resulting polymer particle (A7) -containing dispersion had a water content of 0.05% and a solid content of 10.08%. The volatile components of the obtained polymer particle (A7) -containing epoxy resin composition are shown in Table 2.

Example 9
The same operation as in Example 1 was performed except that the polymer particle (A8) -containing latex obtained in Production Example 8 was used. The resulting polymer particle (A8) -containing dispersion had a water content of 0.06% and a solid content of 11.65%. The volatile components of the resulting polymer particle (A8) -containing epoxy resin composition are shown in Table 2.

(Comparative Example 1)
In a 500 mL glass container kept at 25 ° C., 100 g of MEK as an organic medium (B) component was taken, and 100 g of the polymer particle (A1) -containing latex obtained in Production Example 1 was added and stirred. 40 g of water was added while stirring the resulting mixture of the polymer particle (A1) -containing latex and the organic medium (B), and then 160 g of acetone (solubility in water at 25 ° C .: ∞) was added as the organic medium (C). added. At this time, separation of water from the mixed organic medium layer was not observed.

(Comparative Example 2)
The same operation as in Example 1 was performed except that the polymer particle (A9) -containing latex obtained in Production Example 9 was used. The obtained polymer particle (A9) -containing dispersion had a water content of 0.08% and a solid content of 12.57%. The volatile components of the resulting polymer particle (A9) -containing epoxy resin composition are shown in Table 2.

  All volatile components were around 1%.

  In Comparative Example 1 using acetone as the organic solvent (C), water could not be separated from the latex containing the polymer particles (A).

(Example 10)
110 g of the polymer particle (A1) -containing epoxy resin composition obtained in Example 1 was cured under the above-described curing conditions to obtain a polymer particle (A1) -containing cured epoxy resin.

  As a result of observing the dispersion state of the polymer particles (A1), the polymer particles (A1) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer particle (A1) -containing cured epoxy resin is shown in Table 3.

(Example 11)
120 g of the polymer particle (A1) -containing epoxy resin composition obtained in Example 2 was cured under the above-described curing conditions to obtain a polymer particle (A1) -containing epoxy resin cured product. The polymer particles (A1) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer particle (A1) -containing cured epoxy resin is shown in Table 3.

(Example 12)
The same operation as in Example 10 was performed except that the polymer particle (A2) -containing epoxy resin composition obtained in Example 3 was used. The polymer particles (A2) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer particle (A2) -containing cured epoxy resin is shown in Table 3.

(Example 13)
The same operation as in Example 10 was performed except that the polymer particle (A3) -containing epoxy resin composition obtained in Example 4 was used. The polymer particles (A3) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer particle (A3) -containing cured epoxy resin is shown in Table 3.

(Example 14)
The same operation as in Example 10 was performed except that the polymer particle (A4) -containing epoxy resin composition obtained in Example 5 was used. The polymer particles (A4) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer particle (A4) -containing cured epoxy resin is shown in Table 3.

(Example 15)
The same operation as in Example 10 was performed except that the polymer particle (A5) -containing epoxy resin composition obtained in Example 6 was used. The polymer particles (A5) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer particle (A5) -containing cured epoxy resin is shown in Table 3.

(Example 16)
The same operation as in Example 10 was performed except that the polymer particle (A6) -containing epoxy resin composition obtained in Example 7 was used. The polymer particles (A6) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer particle (A6) -containing cured epoxy resin is shown in Table 3.

(Example 17)
The same operation as in Example 10 was performed except that the polymer particle (A7) -containing epoxy resin composition obtained in Example 8 was used. The polymer particles (A7) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer particle (A7) -containing cured epoxy resin is shown in Table 3.

(Example 18)
The same operation as in Example 10 was performed except that the polymer particle (A8) -containing epoxy resin composition obtained in Example 9 was used. Aggregates of polymer particles (A8) were confirmed in the obtained cured product. The elastic modulus of the polymer particle (A8) -containing cured epoxy resin is shown in Table 3.

(Comparative Example 3)
An epoxy resin composition containing no polymer particles was cured under the above conditions. The elastic modulus of the obtained cured epoxy resin is shown in Table 3.

(Comparative Example 4)
The same operation as in Example 10 was performed except that the polymer particle (A9) -containing epoxy resin composition obtained in Comparative Example 2 was used. The polymer particles (A9) were uniformly dispersed without aggregation in the obtained cured product. The elastic modulus of the polymer resin (A9) -containing cured epoxy resin is shown in Table 3.

  In each of the Examples containing the rubber-like polymer particles, the elastic modulus of the polymer resin (A) -containing cured epoxy resin is reduced as compared with Comparative Example 3 without addition.

  Moreover, compared with the comparative example 4, all Examples have a high rubber content, and the elastic modulus is reduced by adding the same amount.

  As in Example 2, the addition of twice the amount of polymer particles to Example 1 reduces the elastic modulus of the polymer particle (A) -containing cured epoxy resin.

  Among the examples, the polymer particles (A1) and (A4) to (A8), which are difficult to spray dry, have a high rubber content, and thus the effect of reducing the elastic modulus of the cured epoxy resin is remarkable. Such polymer particles (A) are difficult to be blended in an epoxy resin unless this production method is used, and it can be said that this production method is useful.

  Also, since 2-ethylhexyl acrylate polymer and polyorganosiloxane have a lower glass transition temperature than n-butyl acrylate polymer, 2-ethylhexyl acrylate and polyorganosiloxane were used (A4) and (A6). In this case, the elastic modulus of the polymer particle (A) -containing cured epoxy resin can be further reduced than (A1) using n-butyl acrylate.

Claims (4)

The organic medium (B) is mixed with the polymer particle (A) -containing latex,
Furthermore, an organic medium (C) having a lower solubility in water than the organic medium (B) is mixed,
By removing the aqueous layer derived from the polymer particle (A) -containing latex,
A method for producing a dispersion containing polymer particles (A) comprising the polymer particles (A), an organic medium (B) and an organic medium (C),
(Meth) acrylate and aromatic vinyl monomer having a glass transition temperature of 0 ° C. or higher when the polymer particles (A) are rubber particles (a) in the presence of 80% by mass to 100% by mass. And one or more monomers (b) selected from vinyl cyanide monomers (0) to 20% by mass (provided that (a) + (b) is 100% by mass). For producing a dispersion containing polymer particles (A), which is a polymer particle to be produced.   The polymer particle (A) -containing dispersion obtained by the production method according to claim 1 is mixed with a polymerizable organic compound, and then the volatile components including the organic media (B) and (C) are removed. The manufacturing method of a coalesced particle (A) containing resin composition.   The method for producing a polymer particle (A) -containing resin composition according to claim 2, wherein the polymerizable organic compound is an epoxy resin.   Hardened | cured material obtained by hardening | curing the polymer particle (A) containing resin composition obtained with the manufacturing method of Claim 3.