JP2011026503A - Liquid resin composition containing polymer fine particles, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid resin composition containing polymer fine particles that can keep its viscosity at a usable level as a liquid resin composition even when prepared by adding polymer particles of high concentration to a highly viscous liquid resin. <P>SOLUTION: The liquid resin composition containing polymer fine particles includes 100 pts.wt. of a liquid resin (A) and 50-100 pts.wt. of polymer fine particles (B) having a number average particle diameter of 50-500 nm. The polymer fine particles (B) includes a rubber core layer having a glass transition temperature of 0°C or lower located in the innermost part, a rubber surface crosslinked layer located outside the core layer and a coating polymer layer located in the outermost part. The polymer fine particles (B) have a half-value width of 0.5 time or more and 1 time or less of the number average particle diameter in the number distribution of the particle diameter. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a liquid resin composition containing fine polymer particles, more specifically, a liquid resin having a high viscosity and a relatively low viscosity, although a high concentration of fine polymer particles is added to the resin. The present invention relates to a liquid resin composition containing polymer fine particles.

  Patent Document 1 covers an elastic core layer as a liquid resin composition containing polymer fine particles but having a low viscosity, and an intermediate layer containing a liquid resin component and a monomer having two or more double bonds, Polymer fine particles covering the intermediate layer with a shell layer, and the polymer fine particles have a volume average particle diameter (Mv) / number average particle diameter (Mn) of 3 or less, preferably 2.5 or less, more preferably 2.0. Hereinafter, a liquid resin composition containing polymer fine particles dispersed in the form of primary particles, more preferably 1.5 or less, is disclosed, and the preferred particle size of the polymer fine particles is a volume average particle size of 30 to 3000 nm. It is disclosed that the thickness is more preferably 50 to 1000 nm, and that liquid resin compositions having different degrees of dispersion may be mixed and used.

International Publication WO2009 / 034966 Pamphlet

  An object of the present invention is to provide a polymer resin-containing liquid resin composition that can be maintained in a viscosity range that can be used as a liquid resin composition even when polymer particles are added at a higher concentration to a higher viscosity liquid resin. It is to be.

  The present invention maintains the viscosity range that can be used as a liquid resin composition even when polymer fine particles are added at a higher concentration to a higher viscosity liquid resin by using the technique of Patent Document 1 described above. The liquid resin composition containing a polymer fine particle having a specific amount, a specific particle size distribution, and a polymer fine particle having a specific structure, composition, and particle size has a lower viscosity than expected as a weight average value. It was made based on the discovery.

  That is, the present inventors, for example, polymer fine particles in which a liquid resin composition to which polymer fine particles having a small particle size are added and a liquid resin composition to which polymer fine particles having a larger particle size are added are mixed. It has been discovered that the viscosity of the containing liquid resin composition may be specifically lower than any viscosity of the composition before mixing.

  That is, the present invention includes 100 parts by weight of the liquid resin (A) as a main component, and 50 parts by weight to 100 parts by weight of polymer fine particles (B) having a number average particle diameter of 50 nm to 500 nm. The polymer fine particles (B) include at least two layers of a rubber core layer having a glass transition temperature of 0 ° C. or less present inside thereof and a covering polymer layer present on the outermost side, and the rubber core layer is a diene type Polymer fine particle-containing liquid resin composition comprising at least one selected from the group consisting of a rubber polymer, an acrylic rubber polymer, and an organosiloxane rubber polymer, wherein the coating polymer layer is a polymer of a vinyl monomer. The polymer fine particles (B) have a half width of 0.5 to 1 times the number average particle diameter in the number distribution of the particle diameters. Polymer particles containing the liquid resin composition to about.

  Furthermore, the present inventors have a problem that in such a liquid resin composition containing polymer fine particles of the present invention, when polymer fine particles are contained at a high concentration, dilatancy may appear and it becomes very difficult to handle. The present inventors have found that the dilatancy property can be suppressed as compared with a composition having the same concentration. Thus, since the composition of the present invention has low viscosity and dilatancy is suppressed, it can be stirred with low shearing force, can be easily homogenized at the time of blending, and can be transported at high speed. Uniform coating is easy in a short time.

  In a preferred embodiment, the polymer fine particles (B) include a rubber surface cross-linked layer on the outer side of the rubber core layer and on the inner side of the coating polymer layer, and the rubber surface cross-linked layer is a polyfunctional monomer. It is to make a polymer of a monomer for a rubber surface cross-linking layer comprising 30 to 100% by weight and other vinyl monomers of 0 to 70% by weight.

  A preferred embodiment is the polymer fine particle-containing liquid resin composition of the present invention, wherein the polymer fine particle-containing liquid resin composition has a viscosity at 50 ° C. of 500 poise or less.

  A preferred embodiment is the liquid resin composition containing polymer fine particles of the present invention, wherein the polymer fine particles (B) are dispersed in a primary particle state in the liquid resin (A). It is to make a liquid resin composition containing polymer fine particles.

  A preferred embodiment is the polymer fine particle-containing liquid resin composition of the present invention, wherein the polymer fine particle (B) contains two or more maximum values in the particle size distribution of the polymer fine particles (B). It is to make it a liquid resin composition.

  A preferred embodiment is the polymer fine particle-containing liquid resin composition of the present invention, wherein the polymer fine particles (B) 100 wt% is 0.075 to 0.125 μm polymer fine particles (BS) 10 to 90 wt%, And a polymer fine particle-containing liquid resin composition comprising 10 to 90% by weight of polymer fine particles (BL) having a volume average particle diameter of 0.175 to 0.225 μm.

  A preferred embodiment is the polymer fine particle-containing liquid resin composition of the present invention, wherein the liquid fine particle-containing liquid contains 55 to 70% by weight of the liquid resin (A) and 30 to 45% by weight of the polymer fine particles (BS). 100 wt% of resin composition (ABS), 55 wt% to 70 wt% of liquid resin (A), and 100 wt% of liquid resin composition (ABL) containing polymer fine particles (BL) of 30 wt% to 45 wt%. And the viscosity of the polymer fine particle-containing liquid resin composition is the viscosity of the polymer fine particle-containing liquid fat composition (ABS) and the viscosity of the polymer fine particle-containing liquid resin composition (ABL). A liquid resin composition containing polymer fine particles, characterized in that the viscosity is lower than any of the above.

  The present invention also relates to a method for producing the polymer fine particle-containing liquid resin composition of the present invention, wherein the polymer fine particle-containing liquid resin composition (ABS) is 10 to 90% by weight, and the polymer fine particle-containing liquid resin composition. (ABL) It is related with the manufacturing method of a polymer fine particle containing liquid resin composition including the mixing process which mixes 10 to 90 weight%, and obtains 100 weight% of this polymer fine particle containing liquid resin composition.

  The polymer fine particle-containing liquid resin composition of the present invention is a polymer fine particle-containing liquid resin composition containing polymer fine particles having a specific structure, composition, and particle size in a specific amount and with a specific particle size distribution. Even if polymer fine particles are added to the resin at a higher concentration, it can be maintained in a viscosity range that can be used as a liquid resin composition, and the mechanical strength of the resin molded body using the liquid resin according to the present invention as a raw material It is excellent in the improvement effect and the effect of reducing the addition amount when the resin composition of the present invention is used as a master batch for improving the strength, and further has excellent thixotropy.

(Polymer fine particle-containing liquid resin composition)
The polymer fine particle-containing liquid resin composition of the present invention comprises the liquid resin (A) as a main component, 100 parts by weight of the liquid resin (A), and 50 parts by weight of polymer fine particles (B) having a number average particle size of 50 nm to 500 nm. As described later, the polymer fine particles having a specific structure, composition, and particle size are included in a specific particle size distribution, so that the polymer fine particles are added at a high concentration to the high viscosity liquid resin. Nevertheless, it is maintained in a viscosity range that can be used as a liquid resin composition.

  That is, the polymer fine particles (B) according to the present invention include at least two layers of a rubber core layer having a glass transition temperature of 0 ° C. or less present inside thereof and a covering polymer layer present on the outermost side, and the rubber core layer Is at least one selected from the group consisting of diene rubber polymers, acrylic rubber polymers, and organosiloxane rubber polymers, and the coating polymer layer is required to be a polymer of vinyl monomers. Such a coating polymer layer has an effect of improving the dispersibility of the polymer fine particles (B) in the liquid resin (A).

  Further, the polymer fine particles (B) in the composition of the present invention are required to have a half width of 0.5 to 1 times the number average particle diameter in the number distribution of the particle diameters. .

The polymer fine particles (B) preferably include a rubber surface cross-linked layer on the outer side of the rubber core layer and on the inner side of the coating polymer layer,
The rubber surface cross-linked layer is a polymer of a rubber surface cross-linked layer monomer comprising 30 to 100% by weight of a multifunctional monomer and 0 to 70% by weight of other vinyl monomers.
The viscosity range that can be used as the liquid resin composition described above is preferably a viscosity at 50 ° C. of 500 poises or less, and more preferably 200 to 500 poises from the viewpoint of sufficiently obtaining the effects of the present invention. More preferably, it is 300-500 poise, Most preferably, it is 400-500 poise.

  Although the composition of the present invention contains a large amount of polymer fine particles (B), the reason why it has a relatively low viscosity as described above is preferably that in the composition of the present invention, the polymer fine particles (B ) Is dispersed in the state of primary particles in the liquid resin (A).

  From the viewpoint of easily realizing the specific particle size distribution described above, the composition of the present invention is a polymer characterized in that there are two or more maximum values in the number distribution of the particle size of the polymer fine particles (B). It is preferable to use a fine particle-containing liquid resin composition, and from the viewpoint of labor and cost during production, it is more preferable to have 2 to 3 local maximum values, and more preferably 2 local maximum values. Is to make it exist.

  From the viewpoint of satisfactorily obtaining a composition having two such maximum values, 100% by weight of the polymer fine particles (B) in the composition of the present invention is 0.075 to 0.125 μm of polymer fine particles (BS). It is preferable to contain 10 to 90% by weight and 10 to 90% by weight of polymer fine particles (BL) having a volume average particle diameter of 0.175 to 0.225 μm.

From the viewpoint of easily realizing such a particle size distribution for the polymer fine particles in the composition of the present invention, the composition of the present invention is 55 to 70% by weight of the liquid resin (A) and the polymer fine particles (BS). 100% by weight of a polymer fine particle-containing liquid resin composition (ABS) containing 30 to 45% by weight;
It is preferable to use a mixture of 55 to 70% by weight of the liquid resin (A) and 100% by weight of the polymer fine particle-containing liquid resin composition (ABL) containing 30 to 45% by weight of the polymer fine particles (BL). The greatest feature of the invention is that the viscosity of the composition of the present invention which is such a mixture is the viscosity of the polymer fine particle-containing liquid resin composition (ABS) and the viscosity of the polymer fine particle-containing liquid resin composition (ABL). The viscosity is lower than any of the above.

  More specifically, such a composition of the present invention preferably comprises 10 to 90% by weight of the polymer fine particle-containing liquid resin composition (ABS) and the polymer fine particle-containing liquid resin composition (ABL) 10 to 10%. 90% by weight and a mixing step of obtaining 100% by weight of the polymer fine particle-containing liquid resin composition to produce the polymer fine particle-containing liquid resin composition.

  As described above, the polymer fine particle-containing liquid resin composition of the present invention needs to contain 50 to 100 parts by weight of the polymer fine particles (B) with respect to 100 parts by weight of the liquid resin (A). From the viewpoint of sufficiently obtaining the effects of the invention, it is preferably 60 to 80 parts by weight, more preferably 70 to 80 parts by weight.

  As described above, the polymer fine particle-containing liquid resin composition of the present invention is preferably such that the polymer fine particles (B) are dispersed in the liquid resin (A) in the form of primary particles. The polymer fine particles are “dispersed in the state of primary particles” means that the polymer fine particles (B) having a number average particle diameter of 50 nm to 500 nm according to the present invention do not aggregate with each other in the liquid resin (A), It means that they are distributed independently. The dispersion state is obtained by, for example, dissolving a part of the polymer fine particle-containing liquid resin composition of the present invention in a solvent such as methyl ethyl ketone, and measuring the particle diameter with a particle diameter measuring device by laser light scattering. Can be confirmed.

  As described above, since the polymer fine particles (B) according to the present invention are dispersed independently in the liquid resin (A) as described above, the effect of improving the mechanical strength is exhibited. Incompatible with A), that is, it preferably contains a cross-linked polymer. For this purpose, polymer fine particles (B) containing the rubber surface cross-linked layer or polymer fine particles (B) using the rubber core layer as a cross-linked rubber core layer are used. It is preferable to do. In addition, the polymer fine particles (B) according to the present invention are required to have a number average particle diameter of 50 nm to 500 nm from the viewpoint of imparting the effect of improving the mechanical strength, but it is preferably 100 nm to 300 nm. The number average particle diameter of such polymer fine particles can be determined using, for example, a dynamic light scattering method or an electron microscope method.

  In such a polymer fine particle-containing liquid resin composition of the present invention, an aqueous medium dispersion in which polymer fine particles are dispersed in an aqueous medium in order has a solubility in water at 20 ° C. of 5% by mass to 40% by mass. After mixing with an organic solvent and further mixing with excess water, the polymer fine particles are slowly aggregated to obtain a polymer fine particle slow aggregate, and after the polymer fine particle slow aggregate is separated and recovered from the liquid phase, Again, the second step of mixing with the organic solvent for dispersion to obtain the polymer fine particle dispersion in which the polymer fine particles are dispersed in the organic solvent for dispersion, and the polymer fine particle dispersion and the liquid resin (A) were further mixed. Then, it is preferable to prepare by including the third step of distilling off the organic solvent for dispersion to obtain the polymer fine particle-containing liquid resin composition of the present invention. By such a method, the polymer fine particle-containing liquid resin composition in which the polymer fine particles (B) are independently dispersed (hereinafter also referred to as primary dispersion) can be easily obtained. Excellent in properties.

  In the above-described method for producing the polymer fine particle-containing liquid resin composition of the present invention, the aqueous medium dispersion preferably comprises emulsion polymerization, suspension polymerization, miniemulsion polymerization, and dispersion of monomers in the aqueous medium. It is an aqueous latex formed by polymerizing the polymer particles (B) using one or more methods selected from the group consisting of polymerization.

  In such a polymer fine particle-containing liquid resin composition of the present invention, an antioxidant, an ultraviolet absorber, an inorganic filler, a dye, a pigment, a diluent, a coupling agent and the like are within a range in which the mechanical strength is not impaired. Thus, it can be appropriately blended as necessary.

(Liquid resin (A))
The liquid resin (A) according to the present invention is preferably one or more selected from the group consisting of a curable or polymerizable monomer and a curable or polymerizable oligomer from a practical viewpoint, and the effects of the present invention are sufficiently obtained. The weight average molecular weight is preferably 300 to 1000 from the viewpoint of obtaining the above.

  The curable or polymerizable monomer or oligomer is preferably an organic compound containing a functional group having a polymerizable or curing reactivity, and the functional group having a polymerizable or curing reactivity is an epoxy. Selected from the group consisting of groups, oxetane groups, hydroxyl groups, carbon-carbon double bonds, amino groups, imide groups, carboxylic acid groups, carboxylic anhydride groups, cyclic esters, cyclic amides, benzoxazine groups, and cyanate ester groups One or more selected from the above and mixtures thereof are preferred. Among these, an epoxy group, an oxetane group, a phenolic hydroxyl group, a cyclic ester, a cyanate ester group, a benzoxazine group, and a compound having a carbon-carbon double bond are polymerizable, from the viewpoint of utility value as a curable resin. More preferably, a so-called epoxy resin having an epoxy group is particularly preferable. Epoxy resins include bisphenol compounds, hydrogenated bisphenol compounds, phenols or o-cresol novolaks, glycidyl ether substitutions of known basic skeleton compounds such as aromatic amines, polycyclic aliphatic or aromatic compounds, and cyclohexene oxide skeletons. A typical example is a diglycidyl ether of bisphenol A and its condensate, a so-called bisphenol A type epoxy resin.

  The polymer fine particle-containing liquid 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, and an ink. And is preferably used as a toner.

  In the case where the medium is a curable or polymerizable monomer, the polymer fine particle-containing liquid resin composition of the present invention is, for example, a curing agent, a catalyst, an action of heat, light (such as ultraviolet rays), or radiation (such as an electron beam), and It becomes the liquid resin composition containing polymer fine particles of the present invention cured by a known curing method such as a combination thereof. When molding in this case, for example, transfer molding method, injection molding method, casting molding method, coating baking method, rotational molding method, photo-molding method, and hand lay-up molding combined with carbon fiber, glass fiber, etc. Methods, prepreg molding methods, pultrusion molding methods, filament winding molding methods, press molding methods, resin transfer molding (RTM, VaRTM) molding methods, SMC molding methods, and the like, but are not limited thereto.

(Polymer fine particles (B))
The polymer fine particles (B) according to the present invention include at least two layers of a rubber core layer having a glass transition temperature of 0 ° C. or less present inside thereof and a covering polymer layer present on the outermost side thereof, and the rubber core layer includes: One or more selected from the group consisting of a diene rubber polymer, an acrylic rubber polymer, and an organosiloxane rubber polymer, and the coating polymer layer is a polymer of a vinyl monomer. Such a structure composed of the inner rubber core layer and the outermost coated polymer layer is referred to as a core / shell structure, and hence the rubber core layer may be referred to as a core layer and the coated polymer layer may be referred to as a shell layer. .

  Such polymer fine particles (B) are preferably in contact with the rubber core layer on the outside and on the inside of the coating polymer layer, 30 to 100% by weight of a polyfunctional monomer, and other vinyl monomers 0 to 70. A rubber surface cross-linked layer which is a polymer of a monomer for rubber surface cross-linked layer consisting of% by weight is included.

  From the viewpoint of imparting the effect of improving the mechanical strength, the rubber core layer is preferably 40% by weight or more, more preferably 45% by weight to 90% by weight, based on 100% by weight of the polymer fine particles (B). .

  The rubber surface cross-linked layer prevents elution of the polymer fine particles (B) according to the present invention into the liquid resin (A) over a long period of time, and increases the mechanical strength improving effect. From one or more of these viewpoints, which are present uniformly on the outer wall surface of the polymer fine particles, it is preferable to be in contact with the rubber core layer on the outer side and on the inner side of the coating polymer layer. Such a rubber surface cross-linked layer is preferably 20% by weight or less, more preferably 5% by weight to 10% by weight, with the polymer fine particles (B) being 100% by weight, from the above viewpoint.

  The coating polymer layer has a function of enhancing the dispersibility of the polymer fine particles (B) according to the present invention in the liquid resin (A), and the viewpoint of enhancing the dispersibility while sufficiently exhibiting the effect of improving the mechanical strength. Therefore, the amount of the polymer fine particles (B) is preferably 50% by weight or less based on 100% by weight, and more preferably 10% by weight to 45% by weight.

(Rubber core layer)
The rubber core layer is one or more selected from the group consisting of a diene rubber polymer, an acrylic rubber polymer, and an organosiloxane rubber polymer, and is a crosslinked rubber-like polymer having a Tg of 0 ° C. or lower. Is an acrylic rubber polymer.

  The method for introducing such a crosslinked structure is not particularly limited, and a generally used technique can be employed. For example, when a monomer is polymerized to polymerize the above-described diene rubber polymer, acrylic rubber polymer, etc., a diene monomer as a main component thereof, a polyfunctional monomer or mercapto described later on the acrylic monomer, and the like. Examples thereof include a method in which a crosslinkable monomer such as a group-containing compound is added and then polymerized. In addition, as a method for introducing a crosslinked structure into the organosiloxane rubber polymer, a method in which a polyfunctional alkoxysilane compound is partially used at the time of polymerization, or a reactive group such as a vinyl reactive group or a mercapto group is added to a polysiloxane. Introduce into vinyl polymer and then add vinyl polymerizable monomer or organic peroxide to cause radical reaction, or add cross-linkable monomer such as polyfunctional vinyl compound or mercapto group-containing compound to polysiloxane polymer And then polymerizing.

  Specifically, the crosslinked rubber-like polymer preferably has a gel content of 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. In addition, the gel content referred to in the present specification means that 0.5 g of crumb obtained by coagulation and drying is immersed in 100 g of toluene and left to stand at 23 ° C. for 24 hours, and then insoluble and soluble components are separated. The ratio of insoluble matter to the total amount of insoluble matter and soluble matter is meant.

(Rubber surface cross-linked layer)
The rubber surface cross-linked layer comprises 30 to 100% by weight of a monomer having two or more radical double bonds in the same molecule (hereinafter sometimes referred to as “polyfunctional monomer”), and other vinyl monomers 0 to An effect of reducing the viscosity of the liquid resin composition containing polymer fine particles of the present invention, comprising an intermediate polymer layer polymer obtained by polymerizing 70% by weight of a rubber surface cross-linking layer component, and the coating polymer layer as polymer fine particles (B) The present invention is not particularly limited as long as it exhibits any one of the effect of uniformly existing on the outer wall surface and the effect of improving the dispersibility of the polymer fine particles (B) in the liquid resin (A). By having a rubber surface cross-linked layer formed of such a polyfunctional monomer as a main component, the rubber surface cross-linked layer component is added to the coating polymer layer through one of the double bonds of the polyfunctional monomer. The rubber surface cross-linked layer and the coating polymer layer are substantially chemically bonded to each other and graft polymerized to the rubber core layer through the remaining double bonds, so that the rubber surface cross-linked layer and the rubber core are substantially bonded. Chemical bond with the layer. In other words, since many double bonds are arranged in the core, the grafting efficiency of the shell is increased, and the crosslinking density of the core of the polymer fine particles (B) is increased, so that the above three effects are easily obtained. .

(Coating polymer layer)
The coating polymer layer is composed of a coating polymer layer polymer obtained by polymerizing a coating polymer layer component, and particularly if the effect of improving the dispersibility of the polymer fine particles according to the present invention in the medium is exhibited. Without limitation, for example, vinyl polymers obtained by radical polymerization of vinyl monomers having a vinyl group, polyolefins obtained by polymerizing olefin compounds, silicone polymers obtained by condensation polymerization of siloxane compounds, aliphatic polyesters such as polycaprolactone, polyethylene glycol And polyethers such as polypropylene glycol are preferred. Among these, when the vinyl polymer is used as the covering polymer layer, it is preferable because it can be graft-polymerized to the rubber core layer or the rubber surface cross-linked layer.

  In this case, from the viewpoint of chemically bonding to the liquid or solid matrix resin in order to maintain a good dispersion state without aggregation of the polymer fine particles according to the present invention in the cured product or polymer, the vinyl In addition to the vinyl group that forms the main chain of the polymer, an epoxy group, an oxetane group, a hydroxyl group, a carbon-carbon double bond, an amino group, an imide group, a carboxylic acid group, a carboxylic anhydride group, a cyclic ester, a cyclic amide, A reactive group-containing vinyl monomer containing at least one selected from the group consisting of a benzoxazine group and a cyanate ester group is 0.1 wt% to 50 wt% when the coating polymer layer component is 100 wt%. % Content is more preferable.

  For example, from the viewpoint of maintaining a good dispersion state without aggregation of polymer fine particles when an epoxy resin is used as the medium, the coated polymer layer polymer is made of styrene (St) and acrylonitrile ( AN) as a main component and a copolymer having glycidyl methacrylate (GMA) as a main component as the reactive group-containing vinyl monomer is preferable.

(Method for producing polymer fine particles)
The fine polymer particles (B) according to the present invention can be formed by a well-known method, but can be produced in a general aqueous medium. Therefore, the monomer is emulsion polymerization, suspension polymerization, mini-polymer in the aqueous medium. Polymerization is preferably carried out using at least one method selected from the group consisting of emulsion polymerization and dispersion polymerization, and the polymer fine particles (B) according to the present invention, which is an aqueous latex thus formed, are contained in an aqueous medium. It is preferable to produce the polymer fine particle-containing liquid resin composition of the present invention using an aqueous medium dispersion dispersed in a starting material as a starting material. Among the polymerization methods, emulsion polymerization, particularly multistage emulsion polymerization is preferred from the viewpoint of controlling the structure of the polymer fine particles (B).

  As the emulsifier (dispersant) that can be used in the emulsion polymerization, alkyl or aryl sulfonic acid represented by dioctyl sulfosuccinic acid or dodecylbenzene sulfonic acid, alkyl or aryl ether sulfonic acid, alkyl represented by dodecyl sulfate, or Aryl sulfuric acid, alkyl or aryl ether sulfuric acid, alkyl or aryl substituted phosphoric acid, alkyl or aryl ether substituted phosphoric acid, N-alkyl typified by dodecyl sarcosine acid, alkyl typified by oleic acid, stearic acid, etc. Or various acids such as aryl carboxylic acids, alkyl or aryl ether carboxylic acids, anionic emulsifiers (dispersing agents) such as alkali metal salts or ammonium salts of these acids; alkyl or aryl Nonionic emulsifiers such as substituted polyethylene glycol (dispersing agent); polyvinyl alcohol, alkyl substituted cellulose, polyvinyl pyrrolidone, dispersants such as polyacrylic acid derivatives. These emulsifiers (dispersants) may be used alone or in combination of two or more.

  The amount of emulsifier (dispersant) used is preferably reduced as long as the dispersion stability of the aqueous latex of polymer fine particles is not hindered. Moreover, an emulsifier (dispersant) is so preferable that the water solubility is high. When the water solubility is high, the emulsifier (dispersant) can be easily removed by washing with water, and adverse effects on the finally obtained polycondensate can be easily prevented.

(Diene rubber polymer)
The diene rubber polymer is a polymer that is polymerized with a diene monomer as a main component, and can be a copolymer that is polymerized by appropriately mixing other vinyl monomers.

  Examples of the diene monomer (conjugated diene monomer) include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene, and the like. These diene monomers may be used alone or in combination of two or more. Particularly preferred is 1,3-butadiene.

(Acrylic rubber polymer)
The acrylic rubber polymer is a polymer that is polymerized with an acrylic monomer as a main component, and may be a copolymer obtained by mixing other (meth) acrylic monomers and the other vinyl monomers as appropriate. it can.

  As the acrylic monomer, at least one selected from ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and 2-phenoxyethyl acrylate is excellent in impact resistance improvement effect because of its large rubber elasticity. Of these, butyl acrylate (BA) and 2-ethylhexyl acrylate (2-EHA) are particularly preferable.

  Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl. Alkyl (meth) acrylates such as (meth) acrylate and behenyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; Glycidyl (meth) Glycidyl (meth) acrylates such as acrylate and glycidylalkyl (meth) acrylate; alkoxyalkyl (meth) acrylates; allyl (meth) acrylate, allylalkyl (meth) acrylate Arylalkyl (meth) acrylates; monoethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyfunctional, such as tetraethylene glycol di (meth) acrylate (meth) acrylates. These (meth) acrylates may be used alone or in combination of two or more.

  In this specification, (meth) acrylate means acrylate and / or methacrylate.

  The rubber-like polymer constituting the rubber core layer may be a copolymer of the first monomer and a vinyl monomer (second monomer). Examples of vinyl monomers include vinyl arenes such as styrene, α-methylstyrene, monochlorostyrene, dichlorostyrene; vinyl carboxylic acids such as acrylic acid and methacrylic acid; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl chloride Vinyl acetate; vinyl acetate; alkenes such as ethylene, propylene, butylene, and isobutylene; polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene Is mentioned. These vinyl monomers may be used alone or in combination of two or more. Particularly preferred is styrene.

(Organosiloxane rubber polymer)
Preferred examples of the organosiloxane rubber polymer include polysiloxane polymers composed of alkyl or aryl disubstituted silyloxy units such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy and the like. Specifically, a cyclic siloxane represented by 1,3,5,7-octamethylcyclotetrasiloxane (D4), and preferably a linear or branched chain having a weight average molecular weight of 500 to 20,000 or less. A monomer for forming an organosiloxane rubber polymer composed mainly of an organosiloxane oligomer, using a catalyst such as acid, alkali, salt, or fluorine compound, solution polymerization method, suspension polymerization method, emulsion polymerization method Preferably, the polyorganosiloxane particles polymerized by the above method are exemplified. Kill.

  In addition, 100% by weight of the monomer for forming the organosiloxane rubber polymer includes tri- or higher functional alkoxysilanes such as methyltriethoxysilane and tetrapropyloxysilane, and methyl ortho from the viewpoint of forming a crosslinked structure. One or more selected from the group consisting of tri- or higher functional silane condensates such as silicate is preferably contained in an amount of 0 to 20% by weight.

  Further, in 100% by weight of the monomer for forming the organosiloxane rubber polymer, an allyl substituent is introduced into the organosiloxane rubber polymer so that the coating with the coating polymer layer according to the present invention can be easily performed. From the viewpoint of, it contains a bifunctional hydrolyzable group such as mercaptopropyldimethoxymethylsilane, acryloyloxypropyldimethoxymethylsilane, methacryloyloxypropyldimethoxymethylsilane, vinyldimethoxymethylsilane, vinylphenyldimethoxymethylsilane, and vinyl group. It is preferable that the graft crossing agent which is a silane compound is contained in an amount of 0 to 50% by weight.

(Multifunctional monomer)
As the polyfunctional monomer, butadiene is not included, and allyl alkyl (meth) acrylates such as allyl (meth) acrylate and allylalkyl (meth) acrylate; ethylene glycol di (meth) acrylate, 1,3-butanediol di Multifunctional (meth) acrylates such as (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; diallyl phthalate, triallyl cyanurate, tri Examples include allyl isocyanurate (TAIC), glycidyl diallyl isocyanurate, and divinylbenzene. Particularly preferred are allyl methacrylate, triallyl isocyanurate, and divinylbenzene (DVB).

  Preferred for crosslinking of the rubber core layer are allyl methacrylate (AlMA), TAIC, and diallyl phthalate, particularly from the viewpoint of availability, ease of polymerization, and high graft efficiency of the intermediate polymer layer or the coating polymer layer.

  The component of the monomer for the rubber surface cross-linking layer is preferably AlMA, TAIC, 1,3-butanediol di (meth) acrylate, particularly from the viewpoint of viscosity reduction and availability of the fine particle polymer dispersion, and ease of polymerization. DVB.

(Other vinyl monomers)
Examples of the other vinyl monomers include vinyl monomers that are not any of the above-described diene monomers, (meth) acrylic monomers, and multifunctional monomers, and include, for example, styrene, α-methylstyrene, 1- or 2-vinyl. Vinyl aromatic compounds such as naphthalene, monochlorostyrene, dichlorostyrene, bromostyrene; alkenes such as ethylene, propylene, butylene, isobutylene; vinyl cyanide compounds represented by (meth) acrylonitrile; (meth) acrylamide, alkyl vinyl ether These other vinyl monomers may be used alone or in combination of two or more.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these, and can be implemented with appropriate modifications within a range that can meet the gist of the preceding and following descriptions. These are all included in the technical scope of the present invention.

(Evaluation methods)
First, the evaluation method of the polymer fine particle containing liquid resin composition of each Example and a comparative example is demonstrated below.

[1] Measurement of average particle size and degree of dispersion The volume average particle size (Mv) and number average particle size (Mn) of the polymer fine particles dispersed in the aqueous latex and polymer fine particle-containing liquid resin composition are determined by Microtrac UPA150. Measurement was performed using (Nikkiso Co., Ltd.). The aqueous latex was diluted with deionized water, and the liquid resin composition was diluted with methyl ethyl ketone as the measurement sample. For measurement, enter the refractive index of water or methyl ethyl ketone and the refractive index of each polymer particle, and adjust the sample concentration so that the measurement time is 600 seconds and the Signal Level is in the range of 0.6 to 0.8. I went. The degree of dispersion was determined by calculating Mv / Mn from the values of Mv and Mn.

[2] Viscosity measurement The viscosity in the liquid resin composition was measured using a digital viscometer DV-II + Pro type manufactured by BROOKFIELD. Depending on the viscosity region, the spindle CPE-41 or CPE-52 was properly used, and the shear rate was changed as necessary at a measurement temperature of 50 ° C. to measure the viscosity.

  Further, a value obtained by dividing the viscosity value at Shear Rate 10 “1 / s” by the viscosity value at Shear Rate 2 “1 / s” was used as a non-Newtonian scale. When this value is less than 1, the liquid resin composition exhibits thixotropy, and when it exceeds 1, it exhibits dilatancy.

(Production Example 1 of Aqueous Latex Containing Polymer Fine Particles 1: Diene Rubber Polymer 1)
In a pressure-resistant polymerization machine, 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, 0.002 parts by mass of disodium ethylenediaminetetraacetate (EDTA), 0.001 part by mass of ferrous sulfate and heptahydrate Part, and sodium dodecylbenzenesulfonate (SDBS) 1.55 parts by mass, sufficiently nitrogen substitution while stirring to remove oxygen, 100 parts by mass of butadiene (Bd) was introduced into the system, The temperature was raised to 45 ° C. Polymerization was initiated by adding 0.03 parts by mass of paramentane hydroperoxide (PHP), followed by 0.10 parts by mass of sodium formaldehyde sulfoxylate (SFS). 0.03 part by mass of paramentane hydroperoxide (PHP) was added at 3, 5, and 7 hours from the start of polymerization. In addition, 0.0006 parts by mass of EDTA and 0.003 parts by mass of ferrous sulfate / pentahydrate were added at 4, 6 and 8 hours after the start of polymerization. At 15 hours after polymerization, the residual monomer was removed by devolatilization under reduced pressure to complete the polymerization, and an aqueous latex (R-1) containing an elastic core layer mainly composed of polybutadiene rubber was obtained. The volume average particle diameter of the elastic core layer of the polymer fine particles contained in the obtained aqueous latex was 90 nm.

  In a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, 255 parts by mass of an aqueous latex (R-1) containing an elastic core layer mainly composed of the polybutadiene rubber ( Polybutadiene rubber particles (equivalent to 83 parts by mass) and deionized water (58 parts by mass) were charged and stirred at 60 ° C. while purging with nitrogen. After adding 0.004 parts by mass of EDTA, 0.001 part by mass of ferrous sulfate heptahydrate, and 0.2 parts by mass of SFS, 4 parts by mass of triallyl cyanurate (TAIC) and cumene hydroperoxide (CHP) ) 0.07 part by mass was added and stirred for 60 minutes. Thereafter, 5.4 parts by mass of styrene (St), 3.9 parts by mass of acrylonitrile (AN), 0.8 parts by mass of methyl methacrylate (MMA), 6.9 parts by mass of glycidyl methacrylate (GMA), and 0.05 parts by mass of CHP Was added continuously over 110 minutes. After completion of the addition, 0.065 parts by mass of CHP was added, and stirring was further continued for 1 hour to complete the polymerization, thereby obtaining an aqueous latex (L-1) containing polymer fine particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer fine particles contained in the obtained aqueous latex was 100 nm.

(Production Example 2 of Aqueous Latex Containing Polymer Fine Particles: Diene Rubber Polymer 2)
In a pressure-resistant polymerization machine, 7 parts by mass of an aqueous latex (R-1) containing an elastic core layer mainly composed of the polybutadiene rubber obtained in Production Example 1 in terms of solid content, 200 parts by mass of deionized water, tripotassium phosphate 0.03 part by mass, 0.002 part by mass of EDTA, and 0.001 part by mass of ferrous sulfate heptahydrate were added, and after sufficient nitrogen substitution with stirring, oxygen was removed, and butadiene (Bd ) 93 parts by mass were charged into the system and heated to 45 ° C. Polymerization was initiated by adding 0.02 parts by mass of paramentane hydroperoxide (PHP), followed by 0.10 parts by mass of SFS. 0.03 part by mass of PHP, 0.0006 part by mass of EDTA, and 0.003 part by mass of ferrous sulfate and heptahydrate were added every 3 hours from the start of polymerization to 24 hours. At 30 hours after polymerization, the residual monomer was removed by devolatilization under reduced pressure to complete the polymerization, and an aqueous latex (R-2) containing an elastic core layer mainly composed of polybutadiene rubber was obtained. The volume average particle diameter of the elastic core layer of the polymer fine particles contained in the obtained aqueous latex was 195 nm.

  In a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, 255 parts by mass of an aqueous latex (R-2) containing an elastic core layer mainly composed of the polybutadiene rubber ( Polybutadiene rubber particles (equivalent to 83 parts by mass) and deionized water (58 parts by mass) were charged and stirred at 60 ° C. while purging with nitrogen. After adding 0.004 part by mass of EDTA, 0.001 part by mass of ferrous sulfate and heptahydrate, and 0.2 part by mass of SFS, 4 parts by mass of TAIC and 0.07 part by mass of CHP were added and stirred for 60 minutes. Thereafter, a mixture of St 5.4 parts by mass, AN 3.9 parts by mass, MMA 0.8 parts by mass, GMA 6.9 parts by mass, and CHP 0.05 parts by mass was continuously added over 110 minutes. After completion of the addition, 0.065 parts by mass of CHP was added, and stirring was further continued for 1 hour to complete the polymerization, thereby obtaining an aqueous latex (L-2) containing polymer fine particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer fine particles contained in the obtained aqueous latex was 200 nm.

(Production Example 3 of Aqueous Latex Containing Polymer Fine Particles: Diene Rubber Polymer 3)
Into a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, 178.5 parts by mass of the aqueous latex (R-1) obtained in Production Example 1 (polybutadiene rubber particles 58. 1 part by mass), 76.5 parts by mass of the aqueous latex (R-2) obtained in Production Example 2 (equivalent to 24.9 parts by mass of polybutadiene rubber particles), and 58 parts by mass of deionized water were charged, and nitrogen substitution was performed. The mixture was stirred at 60 ° C. After adding 0.004 part by mass of EDTA, 0.001 part by mass of ferrous sulfate and heptahydrate, and 0.2 part by mass of SFS, 4 parts by mass of TAIC and 0.07 part by mass of CHP were added and stirred for 60 minutes. Thereafter, a mixture of St 5.4 parts by mass, AN 3.9 parts by mass, MMA 0.8 parts by mass, GMA 6.9 parts by mass, and CHP 0.05 parts by mass was continuously added over 110 minutes. After completion of the addition, 0.065 parts by mass of CHP was added, and stirring was further continued for 1 hour to complete the polymerization, thereby obtaining an aqueous latex (L-3) containing polymer fine particles. The polymerization conversion rate of the monomer component was 99% or more.

(Production Examples 4 of aqueous latex containing polymer fine particles, 5: Diene rubber polymer 4, 5)
In Production Example 3, 178.5 parts by mass of aqueous latex (R-1) (equivalent to 58.1 parts by mass of polybutadiene rubber particles), 76.5 parts by mass of aqueous latex (R-2) (24.9 parts by mass of polybutadiene rubber particles) In place of water latex (R-1) 127.5 parts by weight (equivalent to 41.5 parts by weight of polybutadiene rubber particles), water latex (R-2) 127.5 parts by weight (polybutadiene rubber particles 41.5 parts by weight) Part) or aqueous latex (R-1) 76.5 parts by weight (polybutadiene rubber particles 24.9 parts by weight), aqueous latex (R-2) 178.5 parts by weight (polybutadiene rubber particles 58.1 parts by weight) Aqueous latexes (L-4) and (L-5) containing polymer fine particles were obtained in the same manner as in Production Example 3, except that the equivalent) was used. The polymerization conversion rate of the monomer component was 99% or more.

  The monomer compositions of Production Examples 1 to 5 are summarized in Table 1 below.

Example 1
126 parts by mass of methyl ethyl ketone (MEK) was introduced into a 1 L mixing tank at 30 ° C., and 126 parts by mass of the aqueous polymer latex latex (L-3) obtained in Production Example 3 was added while stirring. After mixing uniformly, 200 parts (total 452) parts of water was added at a supply rate of 80 parts by weight / minute. When the stirring was stopped immediately after the supply was completed, a slurry liquid containing floating aggregates was obtained. Next, 350 mass parts of liquid phases were discharged | emitted from the discharge outlet of the tank lower part, leaving the aggregate. 150 parts by mass of MEK was added to the obtained aggregate (polymer fine particle dope) and mixed (residual 252) to obtain an organic solvent solution in which the polymer fine particles were dispersed. Into 430 parts by mass of this organic solvent solution (containing 66.7 parts by weight of polymer fine particles), 100 parts by mass of liquid bisphenol A type epoxy resin (“JER828EL” manufactured by JER) was added, and after mixing, MEK was distilled off under reduced pressure. A bisphenol A type epoxy resin in which polymer fine particles were dispersed was obtained as a polymer fine particle-containing liquid resin composition 1.

(Examples 2 and 3)
In Example 1, instead of the polymer fine particle aqueous latex (L-3) obtained in Production Example 3, the polymer fine particle aqueous latex (L-4) obtained in Production Example 4 or obtained in Production Example 5 was used. A bisphenol A type epoxy resin in which polymer fine particles are dispersed is used as polymer fine particle-containing liquid resin compositions 2 and 3 in the same manner as in Example 1 except that the obtained aqueous latex of polymer fine particles (L-5) is used. I got each.

(Comparative Examples 1 and 2)
In Example 1, instead of the polymer fine particle aqueous latex (L-3) obtained in Production Example 3, the polymer fine particle aqueous latex (L-1) obtained in Production Example 1 or obtained in Production Example 2 was used. A bisphenol A type epoxy resin in which polymer fine particles are dispersed is used as polymer fine particle-containing liquid resin compositions 4 and 5 in the same manner as in Example 1 except that the obtained aqueous latex of polymer fine particles (L-2) is used. I got each.

(Comparative Example 3)
100 parts by mass of liquid bisphenol A type epoxy resin (“JER828EL” manufactured by JER) was added to 167 parts by mass of the polymer fine particle-containing liquid resin composition 4 obtained in Comparative Example 1, and stirred at 80 ° C. for polymer particle concentration A 25 wt% polymer fine particle-containing liquid resin composition 6 was obtained.

(Comparative Examples 4-7)
In Comparative Example 3, a polymer concentration of 25 wt% was obtained in the same manner as in Comparative Example 3 except that instead of the polymer fine particle-containing liquid resin composition 4, polymer fine particle-containing liquid resin compositions 1, 2, 3, and 5 were used. Polymer fine particle-containing liquid resin compositions 7, 8, 9, and 10 were obtained.

  Table 2 shows the results of viscosity characteristics measurement of the polymer fine particle-containing liquid resin compositions 1 to 5 obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and the polymer fine particle-containing liquid obtained in Comparative Examples 3 to 7 Table 3 summarizes the results of measurement of the viscosity characteristics of the resin compositions 6 to 10.

  As an example, as shown in Table 2 with respect to the results of Examples 1 to 3, the viscosity value at 50 ° C. of the polymer fine particle-containing liquid resin composition in which large and small particles are mixed is the single polymer of each of the large and small particles of Comparative Examples 1 and 2. It is lower than the viscosity value of the fine particle-containing liquid resin composition. In particular, the viscosity value is less than half that of Comparative Example 1.

  Further, as shown in Table 2, the non-Newtonian property has a value exceeding 1 in Comparative Example 2, that is, a dilatancy property, whereas the large and small particle mixed systems of Examples 1 to 3 have a value of 1 or less. That is, it shows thixotropy.

  From the above, the polymer fine particle-containing liquid resin composition of the present invention has a relatively low viscosity and suppressed dilatancy despite its high concentration, so that liquid transport at high speed is possible. For example, it shows that uniform coating is easy in a short time during coating.

  Further, as shown in Table 3 for the results of Comparative Examples 3 to 7, in the case where the polymer fine particle concentration does not reach 50 parts by mass with respect to 100 parts by mass of the liquid resin, the effect of reducing the viscosity by mixing large and small particles and the non-Newtonian property Improvement effect is not recognized.

Claims (8)

The main component of the liquid resin (A) is 100 parts by weight of the liquid resin (A) and 50 to 100 parts by weight of polymer fine particles (B) having a number average particle size of 50 nm to 500 nm. ) Includes at least two layers of a rubber core layer having a glass transition temperature of 0 ° C. or less present on the inner side thereof and a coating polymer layer existing on the outermost side thereof,
The rubber core layer is at least one selected from the group consisting of a diene rubber polymer, an acrylic rubber polymer, and an organosiloxane rubber polymer;
The coating polymer layer is a polymer resin containing polymer fine particles, wherein the polymer fine particle (B) is a polymer of vinyl monomers, and the polymer fine particles (B) have a number average particle size of 0.5 in the particle size distribution. A liquid resin composition containing polymer fine particles characterized by having a half-value width of not less than 1 and not more than 1 time. The polymer fine particle (B) includes a rubber surface cross-linked layer on the outer side of the rubber core layer and on the inner side of the coating polymer layer,
The polymer according to claim 1, wherein the rubber surface cross-linking layer is a polymer of a rubber surface cross-linking layer monomer composed of 30 to 100% by weight of a polyfunctional monomer and 0 to 70% by weight of other vinyl monomers. A fine particle-containing liquid resin composition.   3. The polymer fine particle-containing liquid resin composition according to claim 1, wherein the polymer fine particle-containing liquid resin composition has a viscosity at 50 ° C. of 500 poise or less.   It is a polymer fine particle containing liquid resin composition in any one of Claims 1-3, Comprising: The said polymer microparticle (B) is disperse | distributing in the state of a primary particle in the said liquid resin (A). A liquid resin composition containing fine polymer particles. The polymer fine particle-containing liquid resin composition according to any one of claims 1 to 4,
2. A polymer fine particle-containing liquid resin composition, wherein there are two or more maximum values in the number distribution of the particle diameter of the polymer fine particles (B). The polymer fine particle-containing liquid resin composition according to claim 5,
The polymer fine particles (B) 100% by weight is 0.075 to 0.125 μm polymer fine particles (BS) 10 to 90% by weight, and the volume average particle diameter is 0.175 to 0.225 μm polymer fine particles (BL) 10. A liquid resin composition containing polymer fine particles, comprising: -90% by weight. The polymer fine particle-containing liquid resin composition according to claim 6,
100% by weight of a liquid resin composition (ABS) containing 55 to 70% by weight of the liquid resin (A) and 30% to 45% by weight of the polymer fine particles (BS).
100 wt% of the liquid resin composition (ABL) containing 55 to 70 wt% of the liquid resin (A) and 30 wt% to 45 wt% of the polymer fine particles (BL);
And a mixture of
The viscosity of the polymer fine particle-containing liquid resin composition is lower than any of the viscosity of the polymer fine particle-containing liquid resin composition (ABS) and the viscosity of the polymer fine particle-containing liquid resin composition (ABL). A liquid resin composition containing fine polymer particles. A method for producing the polymer fine particle-containing liquid resin composition according to claim 7,
10 to 90% by weight of the polymer fine particle-containing liquid resin composition (ABS),
10 to 90 wt% of the polymer fine particle-containing liquid resin composition (ABL),
A method for producing a polymer fine particle-containing liquid resin composition, comprising a mixing step of mixing 100% to obtain 100% by weight of the polymer fine particle-containing liquid resin composition.