JP2022135758A - Separation method and method for producing resin composition - Google Patents

Abstract

To provide a novel method whereby: in a mixture of a resin composition containing polymer fine particles and resin and a water-based liquid, the resin composition and the water-based liquid can be separated from each other efficiently.SOLUTION: The present invention discloses a method whereby: in a mixture of a resin composition containing polymer fine particles (A) and resin (B) and a water-based liquid, the resin composition and the water-based liquid can be separated from each other. The method includes a breaking step for applying stress to the mixture, breaking bubble lumps of the water-based liquid.SELECTED DRAWING: None

Description

The present invention relates to a separation method and a method for producing a resin composition.

Thermosetting resins are used in various fields because they have various excellent properties such as high heat resistance and mechanical strength. Among thermosetting resins, epoxy resins are used in a wide range of applications, for example, as matrix resins for electronic circuit sealants, paints, adhesives, and fiber-reinforced materials. Epoxy resins are excellent in heat resistance, chemical resistance, insulation, etc., but have the problem of insufficient impact resistance, which is a characteristic of thermosetting resins. A method of adding an elastomer to a thermosetting resin is widely used to improve the impact resistance of the thermosetting resin.

Examples of the elastomer include polymer microparticles (for example, crosslinked polymer microparticles). Polymer microparticles can generally have a particle size of less than 1 μm. Here, the polymer microparticle particles produced by collecting several primary particles of polymer microparticles having a particle diameter of less than 1 μm are referred to as secondary particles. Although it is possible to disperse the secondary particles of the polymer fine particles in the thermosetting resin, it is very difficult on an industrial level to disperse the primary particles of the polymer fine particles in the thermosetting resin.

As described above, when a resin composition is obtained by mechanically mixing the secondary particles (granules) of the polymer fine particles and the thermosetting resin, the primary particles of the polymer fine particles are mixed in the resin composition. remains agglomerated. Therefore, there is a problem that the surface appearance of the cured product obtained by curing the obtained resin composition is very poor. Therefore, various production methods have been proposed in which fine polymer particles are dispersed in a thermosetting resin in the form of primary particles.

Patent Document 1 discloses a method for producing a resin composition in which fine polymer particles are dispersed in a resin in the form of primary particles as aggregates from latex. According to the disclosure of Patent Document 1, by washing the aggregate with water, water-soluble impurities can be washed away, and a resin composition with less impurities can be obtained.

International publication WO2020/196921

However, the conventional techniques described above are not sufficient from the viewpoint of efficiently separating water containing impurities from the resin composition, and there is room for further improvement.

One embodiment of the present invention has been made in view of the above problems, and an object thereof is to efficiently separate a resin composition and an aqueous liquid from a mixture of a resin composition containing polymer fine particles and a resin and an aqueous liquid. The object is to provide a novel method that can be well separated.

The present inventor has completed the present invention as a result of intensive studies to solve the above problems.

That is, one embodiment of the present invention includes the following configurations.

[1] A method of separating a resin composition and an aqueous liquid from a mixture of a resin composition containing polymer fine particles (A) and a resin (B) and an aqueous liquid,
The mixture includes the resin composition encapsulating the water-based liquid mass,
A separation method, comprising a foam-breaking step of breaking the lumps of the aqueous liquid by applying stress to the mixture.
[2] The foam breaking step includes applying stress to the mixture by thinning the mixture, and applying stress to the mixture by extruding or sucking the mixture through a nozzle having holes. The separation method according to [1], comprising at least one step selected from the group consisting of:
[3] The separation method according to [1] or [2], wherein the viscosity of the mixture is 100 mPa·s or more at 25°C, and the viscosity of the aqueous liquid is less than 100 mPa·s at 25°C.
[4] Any one of [1] to [3], wherein the fine polymer particles (A) are a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body. or the separation method according to one.
[5] The graft portion is derived, as a structural unit, from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers. The separation method according to [4], wherein the polymer comprises a structural unit.
[6] The separation method according to [4] or [5], wherein the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber.
[7] The resin (B) is a liquid, a semisolid, or a solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25° C. [1] to [6 ] The separation method according to any one of .
[8] The separation method according to any one of [1] to [7], wherein the resin (B) is an epoxy resin.
[9] A method for producing a resin composition containing fine polymer particles (A) and a resin (B), comprising the separation method according to any one of [1] to [8] as one step.

According to one aspect of the present invention, it is possible to provide a novel method capable of efficiently separating a resin composition and an aqueous liquid from a mixture of a resin composition containing polymer fine particles and a resin and an aqueous liquid. can.

An embodiment of the invention will be described below, but the invention is not limited thereto. The present invention is not limited to each configuration described below, and various modifications are possible within the scope of the claims. Further, embodiments or examples obtained by appropriately combining technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the scientific literatures and patent documents described in this specification are used as references in this specification. In addition, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)".

[1. Technical idea of the present invention]
In the process of producing a resin composition in which fine polymer particles are dispersed in a resin in the form of primary particles, it may be necessary to separate the resin composition from water (aqueous liquid) containing impurities. If this separation is not properly performed, water containing impurities may eventually be mixed into the resin composition. Aqueous liquids present in resin compositions are known to cause deterioration in productivity and quality in various fields.

A resin composition containing fine polymer particles can have a high viscosity, and in particular, a resin composition containing a relatively high concentration of fine polymer particles (also referred to as a masterbatch) can have a high viscosity. In addition, a resin composition containing fine polymer particles may be viscous (also referred to as adhesiveness). adhesive). Separation of the resin composition and the water-based liquid is generally more difficult as the difference in viscosity between the two and the viscosity of the resin composition increases, so the separation method is limited to a specific method.

The present inventors found that, surprisingly, a highly viscous and highly viscous resin composition, such as the resin composition according to one embodiment of the present invention, can enclose a water-based liquid in the resin composition. We have independently found that the water-based liquid entrained within the composition can exist as one or more masses within the resin composition. In addition, the present inventors have found that such water-based liquid masses in the resin composition cannot be easily separated by conventional methods, and that they remain included in the resin composition even after various conventional washing processes. We have independently found that it can be up to, ie, very difficult to remove.

Therefore, the present inventors have made intensive studies to provide a novel method capable of efficiently separating a resin composition and an aqueous liquid from a mixture of a resin composition containing polymer fine particles and a resin and an aqueous liquid. gone. More specifically, the present inventors have made intensive studies to provide a novel method for easily removing lumps of water-based liquid contained in the resin composition. As a result, the present inventors have independently found the following knowledge and completed the present invention: By applying stress to a resin composition containing a mass of an aqueous liquid, the mass is broken. The water-based liquid exposed on the resin composition can be easily removed.

[2. Separation method]
A separation method according to one embodiment of the present invention is a method of separating a resin composition and an aqueous liquid from a mixture of a resin composition containing polymer fine particles (A) and a resin (B) and an aqueous liquid. wherein the mixture contains the resin composition enclosing the water-based liquid mass, and applying stress to the mixture breaks the water-based liquid mass contained in the mixture. Includes a foam-breaking step. The separation method according to one embodiment of the present invention may be hereinafter referred to as "this separation method".

According to this separation method, the resin composition and the aqueous liquid can be efficiently separated. More specifically, according to the present separation method, by breaking the bubbles of the water-based liquid (free water) that is present in a state of being caught in the resin composition, the resin can be efficiently separated by a simple method. The composition and water-based liquid can be separated.

Hereinafter, the polymer fine particles (A), the resin (B), and the mixture of the resin composition and the aqueous liquid used in this separation method will be described in detail, and then each step of this separation method will be described.

(2-1. Polymer microparticles (A))
Other aspects of the polymer microparticles (A) are not particularly limited as long as they are microparticles obtained by polymerization.

(Graft part)
The polymer microparticles (A) preferably have a graft portion. As used herein, the term "graft portion" intends a polymer grafted to any polymer. The polymer fine particles (A) having a graft portion can also be said to be a graft copolymer. That is, the fine polymer particles (A) are preferably graft copolymers.

The graft portion contains, as structural units, structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers. It is preferably (including) a polymer. A graft section having the above configuration can serve a variety of purposes. "Various roles" include, for example, (a) improving the compatibility between the polymer fine particles (A) and the resin (B), and (b) the performance of the polymer fine particles (A) in the resin (B). and (c) enabling the fine polymer particles (A) to be dispersed in the state of primary particles in the resin composition or its cured product.

Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

Specific examples of vinyl cyan monomers include acrylonitrile and methacrylonitrile.

Specific examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxybutyl (meth)acrylate. By (meth)acrylate is intended herein acrylate and/or methacrylate.

One or more monomers selected from the group consisting of the above-mentioned aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers may be used alone, Two or more kinds may be used in combination.

In the graft portion, as structural units, a structural unit derived from an aromatic vinyl monomer, a structural unit derived from a vinyl cyanide monomer, and a structural unit derived from a (meth)acrylate monomer are combined to form a graft portion 100 In % by weight, preferably 10 to 95% by weight, more preferably 30 to 92% by weight, more preferably 50 to 90% by weight, particularly preferably 60 to 87% by weight, 70 to Most preferably it contains 85% by weight.

The graft portion preferably contains, as a structural unit, a structural unit derived from a monomer having a reactive group. The monomer having a reactive group includes an epoxy group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group. It is preferably a monomer having one or more reactive groups selected from the group consisting of epoxy groups, hydroxyl groups, and having one or more reactive groups selected from the group consisting of carboxylic acid groups A monomer is more preferable, and a monomer having an epoxy group is most preferable. According to the above configuration, the grafted portion of the fine polymer particles (A) and the resin (B) (for example, thermosetting resin) can be chemically bonded in the resin composition. Thereby, the fine polymer particles (A) can be maintained in a good dispersed state without agglomeration of the fine polymer particles (A) in the resin composition or the cured product thereof.

Specific examples of epoxy group-containing monomers include glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and allyl glycidyl ether.

Specific examples of monomers having a hydroxyl group include, for example, (a) 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxy straight-chain alkyl (meth)acrylates; Acrylates (especially hydroxy linear C1-6 alkyl (meth)acrylates); (b) caprolactone-modified hydroxy (meth)acrylates; (c) methyl α-(hydroxymethyl)acrylate, ethyl α-(hydroxymethyl)acrylate hydroxy-branched alkyl (meth)acrylates such as; (d) mono(meth)acrylates of polyester diols (particularly saturated polyester diols) obtained from dihydric carboxylic acids (such as phthalic acid) and dihydric alcohols (such as propylene glycol); hydroxyl group-containing (meth)acrylates, and the like.

Specific examples of monomers having a carboxylic acid group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. As the monomer having a carboxylic acid group, the monocarboxylic acid is preferably used.

Only one type of the above-described monomer having a reactive group may be used, or two or more types may be used in combination.

The graft portion preferably contains 0.5 to 90% by weight, more preferably 1 to 50% by weight, of structural units derived from a monomer having a reactive group in 100% by weight of the graft portion. It is more preferable to contain up to 35% by weight, particularly preferably 3 to 20% by weight. When the graft portion contains (a) 0.5% by weight or more of structural units derived from a monomer having a reactive group in 100% by weight of the graft portion, the resulting resin composition has sufficient impact resistance. and (b) when it contains 90% by weight or less, the resulting resin composition can provide a cured product having sufficient impact resistance, and the resin composition has the advantage of good storage stability.

A structural unit derived from a monomer having a reactive group is preferably contained in the graft portion, and more preferably contained only in the graft portion.

The graft part may contain a structural unit derived from a polyfunctional monomer as a structural unit. When the graft portion contains a structural unit derived from a polyfunctional monomer, (a) swelling of the polymer fine particles (A) in the resin composition can be prevented, and (b) viscosity of the resin composition (c) dispersibility of the fine polymer particles (A) in the resin (D) (e.g., thermosetting resin) is improved, etc. has the advantage of

When the graft portion does not contain a structural unit derived from a polyfunctional monomer, the obtained resin composition has better toughness and A cured product having better impact resistance can be provided.

A polyfunctional monomer can also be said to be a monomer having two or more radically polymerizable reactive groups in the same molecule. Said radically polymerizable reactive group is preferably a carbon-carbon double bond. Examples of polyfunctional monomers include (meth)acrylates having an ethylenically unsaturated double bond, such as allylalkyl (meth)acrylates and allyloxyalkyl (meth)acrylates, butadiene is not included. be done. Examples of monomers having two (meth)acrylic groups include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and cyclohexanedimethanol. Di(meth)acrylates, and polyethylene glycol di(meth)acrylates. Examples of the polyethylene glycol di(meth)acrylates include triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, and the like. are exemplified. Further, as monomers having three (meth)acrylic groups, alkoxylated trimethylolpropane tri(meth)acrylates, glycerolpropoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxy Ethyl)isocyanurate tri(meth)acrylate and the like are exemplified. Alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate and trimethylolpropane triethoxy tri(meth)acrylate. Furthermore, examples of monomers having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like. Furthermore, dipentaerythritol penta(meth)acrylate etc. are illustrated as a monomer which has five (meth)acrylic groups. Furthermore, examples of monomers having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate. Polyfunctional monomers also include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like.

Among the polyfunctional monomers described above, polyfunctional monomers that can be preferably used for polymerization of the graft portion include allyl methacrylate, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and butanediol. Di(meth)acrylates, hexanediol di(meth)acrylates, cyclohexanedimethanol di(meth)acrylates, and polyethylene glycol di(meth)acrylates. Only one type of these polyfunctional monomers may be used, or two or more types may be used in combination.

The graft portion preferably contains 1 to 20% by weight, more preferably 5 to 15% by weight, of the structural unit derived from the polyfunctional monomer in 100% by weight of the graft portion.

In the polymerization of the graft portion, the above monomers may be used alone or in combination of two or more. In addition, the graft portion may contain, as structural units, structural units derived from other monomers in addition to the structural units derived from the monomers described above.

Also, the graft portion is preferably a polymer graft-bonded to an elastic body, which will be described later.

(Glass transition temperature of graft portion)
The glass transition temperature of the graft portion is preferably 190°C or lower, more preferably 160°C or lower, more preferably 140°C or lower, more preferably 120°C or lower, preferably 80°C or lower, more preferably 70°C or lower, and 60°C. The following is more preferable, 50° C. or less is more preferable, 40° C. or less is more preferable, 30° C. or less is more preferable, 20° C. or less is more preferable, 10° C. or less is more preferable, 0° C. or less is more preferable, and −20° C. The following is more preferable, -40°C or less is more preferable, -45°C or less is more preferable, -50°C or less is more preferable, -55°C or less is more preferable, -60°C or less is more preferable, -65°C or less is More preferably -70°C or less, more preferably -75°C or less, more preferably -80°C or less, more preferably -85°C or less, more preferably -90°C or less, more preferably -95°C or less , -100°C or lower is more preferred, -105°C or lower is more preferred, -110°C or lower is more preferred, -115°C or lower is more preferred, -120°C or lower is even more preferred, and -125°C or lower is particularly preferred.

The glass transition temperature of the graft portion is preferably 0° C. or higher, more preferably 30° C. or higher, more preferably 50° C. or higher, more preferably 70° C. or higher, still more preferably 90° C. or higher, and particularly preferably 110° C. or lower. preferable.

The Tg of the graft portion can be determined by the composition of the constituent units contained in the graft portion. In other words, the Tg of the obtained graft portion can be adjusted by changing the composition of the monomers used when manufacturing (polymerizing) the graft portion.

The Tg of the graft portion can be obtained by performing viscoelasticity measurement using a flat plate made of polymer fine particles (A). Specifically, Tg can be measured as follows: (1) For a flat plate made of polymer fine particles (A), a dynamic viscoelasticity measuring device (eg, DVA-200 manufactured by IT Keisoku Co., Ltd.) ) is used to perform dynamic viscoelasticity measurement under tensile conditions to obtain a tan δ graph; (2) Regarding the obtained tan δ graph, the tan δ peak temperature is taken as the glass transition temperature. Here, in the graph of tan δ, when a plurality of peaks are obtained, the highest peak temperature is taken as the glass transition temperature of the graft portion.

(Graft ratio of graft part)
In one embodiment of the present invention, the polymer fine particle (A) is a polymer having the same structure as the graft portion and is not graft-bonded to any polymer (for example, an elastic body described later). may have In the present specification, "a polymer having the same structure as the graft portion and not grafted to any polymer" is also referred to as a non-grafted polymer. The non-grafted polymer also constitutes part of the fine polymer particles (A) according to one embodiment of the present invention. The non-graft polymer can also be said to be a polymer that is not graft-bonded to any polymer among the polymers produced in the polymerization of the graft portion.

In the present specification, the proportion of the polymer grafted to an arbitrary polymer, that is, the proportion of the grafted portion, among the polymers produced in the polymerization of the grafted portion is referred to as the graft rate. The graft ratio can also be said to be a value represented by (weight of grafted portion)/{(weight of grafted portion)+(weight of non-grafted polymer)}×100.

The graft ratio of the graft portion is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When the graft ratio is 70% or more, there is an advantage that the viscosity of the resin composition does not become too high.

In the present specification, the method for calculating the graft ratio is as follows. First, an aqueous latex containing the polymer microparticles (A) is obtained, and then powder particles of the polymer microparticles (A) are obtained from the aqueous latex. Specifically, the method for obtaining the powdery particles of the polymer microparticles (A) from the aqueous latex includes (a) coagulating the polymer microparticles (A) in the aqueous latex, and (b) obtaining the coagulated A method of dehydrating the substance and (c) further drying the coagulate to obtain powdery particles of the polymer fine particles (A) can be mentioned. Next, 2 g of powder particles of polymer fine particles (A) are dissolved in 50 mL of methyl ethyl ketone (hereinafter also referred to as MEK). After that, the obtained MEK melt is separated into a component soluble in MEK (MEK soluble matter) and a component insoluble in MEK (MEK insoluble matter). Specifically, the following (1) to (3) are performed: (1) Using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E), the rotation speed was 30,000 rpm for 1 hour. subjecting the MEK lysate to centrifugation to separate the lysate into MEK soluble and MEK insoluble; (2) mixing the obtained MEK soluble and MEK and separating the obtained MEK mixture Using the above-mentioned centrifuge, subjecting it to centrifugation at a rotation speed of 30,000 rpm for 1 hour to separate the MEK mixture into MEK soluble matter and MEK insoluble matter; (3) the operation of (2) above. Repeat once (i.e. perform a total of 3 centrifugation runs). A concentrated MEK soluble matter is obtained by such an operation. 20 ml of the concentrated MEK solubles are then mixed with 200 ml of methanol. An aqueous calcium chloride solution of 0.01 g of calcium chloride dissolved in water is added to the resulting mixture and the resulting mixture is stirred for 1 hour. Thereafter, the resulting mixture is separated into a methanol-soluble portion and a methanol-insoluble portion, and the weight of the methanol-insoluble portion is defined as the free polymer (FP) amount.

The graft ratio is calculated from the following formula.
Graft rate (%)=100-[(FP amount)/{(FP amount)+(MEK-insoluble weight)}]/(weight of polymer in graft portion)×10,000.

The weight of the polymer other than the graft portion is the charged amount of the monomer constituting the polymer other than the graft portion. A polymer other than the graft portion is, for example, an elastic body. Moreover, when the fine polymer particles (A) contain a surface-crosslinked polymer, which will be described later, the polymer other than the graft portion contains both the elastic body and the surface-crosslinked polymer. The weight of the polymer of the graft portion is the charged amount of the monomers constituting the polymer of the graft portion. In calculating the graft ratio, the method of coagulating the fine polymer particles (A) is not particularly limited, and a method using a solvent, a method using a coagulant, a method of spraying an aqueous latex, or the like can be used.

(Modified example of graft part)
In one embodiment of the present invention, the graft portion may consist of only one type of graft portion having structural units of the same composition. In one embodiment of the present invention, the graft portion may consist of a plurality of types of graft portions each having a different composition of structural units.

In one embodiment of the present invention, a case where the graft portion is composed of a plurality of types of graft portions will be described. In this case, each of the plurality of types of graft portions is designated as graft portion ₁ , graft portion ₂ , . . . , graft portion _n (n is an integer of 2 or more). The graft portion may comprise a composite of graft portion _{1 1} , graft portion _{2 2} , . . . , and graft portion _n , each polymerized separately. The graft portion may contain one polymer obtained by sequentially polymerizing graft portion _{1 1} , graft portion _{2 2} , . . . , and graft portion _n . Such polymerization of a plurality of polymerized portions (graft portions) in order is also referred to as multi-stage polymerization. A polymer obtained by multistage polymerization of a plurality of types of graft portions is also referred to as a multistage polymerization graft portion. A method for producing the multistage polymerized graft portion will be described in detail later.

When the graft portion is composed of multiple types of graft portions, not all of these multiple types of graft portions may be graft-bonded to the elastic body. At least a part of at least one type of graft portion may be graft-bonded to the elastic body, and other types (a plurality of other types) of graft portions are graft portions that are graft-bonded to the elastic body. may be grafted to. Further, when the graft portion is composed of a plurality of types of graft portions, a plurality of types of polymers that are polymers having the same configuration as the plurality of types of graft portions and are not graft-bonded to the elastic body graft polymer).

A multistage polymerized graft portion composed of graft portion ₁ , graft portion ₂ , . . . , and graft portion _n will be described. In the multi-stage polymerized graft portion, the graft portion _n may cover at least a portion of the graft portion _n-1 , or may cover the entirety of the graft portion _n-1 . In the multi-stage polymerized graft portion, a part of the graft portion _n may be inside the graft portion _n−1 .

In the multi-stage polymerized graft portion, each of the plurality of graft portions may form a layered structure. For example, when the multistage polymerized graft portion is composed of graft portion ₁ , graft portion ₂ , and graft portion ₃ , graft portion ₁ forms the innermost layer in the graft portion, and graft portion ₂ is formed on the outer side of graft portion ₁ . Further, an aspect in which the layer of the graft portion ₃ is formed as the outermost layer outside the layer of the graft portion ₂ is also an aspect of the present invention. Thus, a multi-stage polymerized graft portion in which each of a plurality of graft portions forms a layered structure can also be called a multi-layer graft portion. That is, in one embodiment of the present invention, the graft portion may include (a) a composite of multiple types of graft portions, (b) a multi-stage polymerization graft portion and/or (c) a multi-layer graft portion.

When an arbitrary polymer (for example, an elastic body described later) and the graft portion are polymerized in this order in the production of the polymer fine particles (A), at least part of the graft portion in the resulting polymer fine particles (A) is At least a portion of any polymer may be coated. In other words, the arbitrary polymer and the graft portion are polymerized in this order, which means that the arbitrary polymer and the graft portion are polymerized in multiple stages. The polymer microparticles (A) obtained by multistage polymerization of an arbitrary polymer and a graft portion can also be said to be a multistage polymer.

When the polymer microparticles (A) are a multistage polymer, the graft portion may coat at least a portion of any polymer (for example, an elastic body to be described later), or may entirely coat any polymer. When the polymer microparticles (A) are multi-stage polymers, part of the graft part may enter inside any polymer. At least a portion of the graft portion preferably covers at least a portion of the elastic body. In other words, at least part of the graft portion is preferably present on the outermost side of the fine polymer particles (A).

When the fine polymer particles (A) are a multi-stage polymer, any polymer (for example, an elastic body to be described later) and the graft portion may form a layered structure. For example, an embodiment in which the elastic body forms the innermost layer (also referred to as a core layer) and the layer of the graft portion is formed as the outermost layer (also referred to as a shell layer) on the outside of the elastic body is also an aspect of the present invention. be. A structure in which an elastic body is used as a core layer and a graft portion is used as a shell layer can be called a core-shell structure. Thus, the polymer fine particles (A) in which the elastic body and the graft part form a layered structure (core-shell structure) can be called a multi-layered polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particle (A) may be a multi-stage polymer and/or a multi-layer polymer or core-shell polymer. However, the fine polymer particles (A) are not limited to the above configuration as long as they have a graft portion.

(elastic body)
It is preferable that the polymer fine particles (A) further have an elastic body. The above-mentioned graft portion is preferably a polymer grafted to the elastic body. That is, the fine polymer particles (A) are more preferably a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body. When the polymer fine particles (A) are a rubber-containing graft copolymer, there is an advantage that the polymer fine particles (A) can be dispersed in the state of primary particles in the resin composition or its cured product. An embodiment of the present invention will be described below, taking as an example the case where the polymer fine particles (A) are a rubber-containing graft copolymer.

The elastic body preferably contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber. The elastic body may contain natural rubber in addition to the rubbers described above. The elastic body can also be called an elastic portion or a rubber particle.

A case (Case A) in which the elastic body contains a diene rubber will be described. In Case A, the resulting resin composition can provide a cured product with excellent toughness and impact resistance. A cured product having excellent toughness and/or impact resistance can also be said to be a cured product having excellent durability.

The diene-based rubber is an elastic body containing, as a structural unit, a structural unit derived from a diene-based monomer. The diene-based monomer can also be called a conjugated diene-based monomer. In case A, the diene rubber contains 50 to 100% by weight of structural units derived from a diene monomer out of 100% by weight of structural units, and a diene monomer other than a diene monomer copolymerizable with a diene monomer. 0 to 50% by weight of a structural unit derived from a vinyl-based monomer. In Case A, the diene-based rubber may contain structural units derived from (meth)acrylate-based monomers as structural units in an amount smaller than the structural units derived from diene-based monomers.

Examples of diene monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene) and 2-chloro-1,3-butadiene. These diene-based monomers may be used alone or in combination of two or more.

Vinyl-based monomers other than diene-based monomers copolymerizable with diene-based monomers (hereinafter also referred to as vinyl-based monomers A) include, for example, styrene, α-methylstyrene, and monochlorostyrene. Vinylarenes such as , dichlorostyrene; Vinylcarboxylic acids such as acrylic acid and methacrylic acid; Vinyl cyanides such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; , propylene, butylene, and isobutylene; and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The vinyl-based monomer A described above may be used alone or in combination of two or more. Among the vinyl-based monomers A described above, styrene is particularly preferable. In addition, in the diene-based rubber in Case A, the structural unit derived from the vinyl-based monomer A is an optional component. In case A, the diene-based rubber may be composed only of structural units derived from diene-based monomers.

In Case A, the diene-based rubber may be butadiene rubber (also referred to as polybutadiene rubber) composed of structural units derived from 1,3-butadiene, or butadiene- Styrene rubber (also called polystyrene-butadiene) is preferred, and butadiene rubber is more preferred. According to the above configuration, the polymer fine particles (A) containing the diene rubber can more effectively exhibit the desired effects. In addition, butadiene-styrene rubber is more preferable in that the transparency of the resulting cured product can be enhanced by adjusting the refractive index.

A case (Case B) in which the elastic body contains (meth)acrylate rubber will be described. In case B, a wide variety of elastomeric polymer designs are possible by combining a wide variety of monomers.

The (meth)acrylate rubber is an elastic body containing, as a structural unit, a structural unit derived from a (meth)acrylate monomer. In case B, the (meth)acrylate rubber contains 50 to 100% by weight of structural units derived from a (meth)acrylate monomer in 100% by weight of the structural units, and It may contain 0 to 50% by weight of constitutional units derived from vinyl monomers other than polymerizable (meth)acrylate monomers. In Case B, the (meth)acrylate-based rubber may contain structural units derived from a diene-based monomer in an amount smaller than the structural units derived from the (meth)acrylate-based monomer. good.

Examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and dodecyl (meth)acrylate. , Alkyl (meth)acrylates such as stearyl (meth)acrylate and behenyl (meth)acrylate; Aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; ) acrylate, hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate; glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidylalkyl (meth)acrylate; alkoxyalkyl (meth)acrylates; Allylalkyl (meth)acrylates such as allyl (meth)acrylate and allylalkyl (meth)acrylate; monoethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, etc. Examples include polyfunctional (meth)acrylates. These (meth)acrylate monomers may be used alone or in combination of two or more. Among these (meth)acrylate monomers, ethyl (meth)acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and butyl (meth)acrylate is more preferred.

In Case B, the (meth)acrylate rubber is preferably one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber and 2-ethylhexyl (meth)acrylate rubber. , butyl (meth)acrylate rubber is more preferred. Ethyl (meth)acrylate rubber is rubber composed of structural units derived from ethyl (meth)acrylate, butyl (meth)acrylate rubber is rubber composed of structural units derived from butyl (meth)acrylate, and 2-ethylhexyl ( A meth)acrylate rubber is a rubber composed of structural units derived from 2-ethylhexyl (meth)acrylate. According to this configuration, the glass transition temperature (Tg) of the elastic body is lowered, so that the polymer fine particles (A) and the resin composition having a low Tg can be obtained. As a result, (a) the resulting resin composition can provide a cured product having excellent toughness, and (b) the viscosity of the resin composition can be made lower.

As the vinyl-based monomer other than the (meth)acrylate-based monomer copolymerizable with the (meth)acrylate-based monomer (hereinafter also referred to as vinyl-based monomer B), the vinyl-based monomer The monomers listed in Form A are included. (Only one type of vinyl-based monomer B may be used, or two or more types may be used in combination. Among vinyl-based monomers B, styrene is particularly preferable. Note that in case B, In the (meth)acrylate-based rubber, the structural unit derived from the vinyl-based monomer B is an optional component.In the case B, the (meth)acrylate-based rubber has a structural unit derived from the (meth)acrylate-based monomer. It may consist of only

A case (Case C) in which the elastic body contains an organosiloxane rubber will be described. In Case C, the resulting resin composition has sufficient heat resistance and can provide a cured product with excellent impact resistance at low temperatures.

Organosiloxane-based rubbers include, for example, (a) dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy, etc., composed of alkyl- or aryl-disubstituted silyloxy units. Organosiloxane-based polymers, (b) organosiloxane-based polymers composed of alkyl or aryl monosubstituted silyloxy units such as organohydrogensilyloxy in which some of the side chain alkyl groups are substituted with hydrogen atoms; be done. These organosiloxane polymers may be used alone or in combination of two or more.

In this specification, a polymer composed of dimethylsilyloxy units is referred to as dimethylsilyloxy rubber, and a polymer composed of methylphenylsilyloxy units is referred to as methylphenylsilyloxy rubber. Polymers composed of oxy units are called dimethylsilyloxy-diphenylsilyloxy rubbers. In the case C, the organosiloxane-based rubbers include dimethylsilyloxy rubber and methylphenylsilyl, since the resin composition containing (a) the obtained granules can provide a cured product or a molded product having excellent heat resistance. It is preferably one or more selected from the group consisting of oxyrubber and dimethylsilyloxy-diphenylsilyloxyrubber, and (b) dimethylsilyloxyrubber is preferred because it is readily available and economical. more preferred.

In case C, the fine polymer particles (A) preferably contain 80% by weight or more, more preferably 90% by weight or more, of the organosiloxane rubber in 100% by weight of the elastic material contained in the fine polymer particles (A). It is more preferable to have According to the configuration, the obtained resin composition can provide a cured product having excellent heat resistance.

The elastic body may further contain an elastic body other than diene rubber, (meth)acrylate rubber and organosiloxane rubber. Examples of elastic bodies other than diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers include natural rubbers.

In one embodiment of the present invention, the elastomer is butadiene rubber, butadiene-styrene rubber, butadiene-(meth)acrylate rubber, ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, 2-ethylhexyl (meth)acrylate rubber. , dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenylsilyloxy rubber, preferably one or more selected from the group consisting of butadiene rubber, butadiene-styrene rubber, butyl (meth)acrylate It is more preferably one or more selected from the group consisting of rubber and dimethylsilyloxy rubber.

(Crosslinked structure of elastic body)
From the viewpoint of maintaining the dispersion stability of the polymer fine particles (A) in the thermosetting resin, it is preferable that a crosslinked structure is introduced into the elastic body. As a method for introducing a crosslinked structure into the elastic body, a generally used method can be adopted, and examples thereof include the following methods. That is, in the production of the elastic body, a monomer capable of constituting the elastic body is mixed with a cross-linkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound, and then polymerized. . In this specification, manufacturing a polymer such as an elastomer is also referred to as polymerizing the polymer.

Methods for introducing a crosslinked structure into an organosiloxane rubber include the following methods: (A) when polymerizing an organosiloxane rubber, a polyfunctional alkoxysilane compound and another material are combined; (B) introducing a reactive group (e.g., (a) a mercapto group and (b) a reactive vinyl group, etc.) into an organosiloxane rubber, and then adding (a) a method of adding an organic peroxide or (b) a polymerizable vinyl monomer or the like for a radical reaction, or (C) a polyfunctional monomer when polymerizing an organosiloxane rubber; and/or a method of mixing a crosslinkable monomer such as a mercapto group-containing compound with other materials, followed by polymerization, and the like.

Examples of the polyfunctional monomer include the polyfunctional monomers exemplified in the section of (graft portion) described above.

Mercapto group-containing compounds include alkyl group-substituted mercaptans, allyl group-substituted mercaptans, aryl group-substituted mercaptans, hydroxy group-substituted mercaptans, alkoxy group-substituted mercaptans, cyano group-substituted mercaptans, amino group-substituted mercaptans, silyl group-substituted mercaptans, and acid group-substituted mercaptans. mercaptans, halo group-substituted mercaptans, acyl group-substituted mercaptans, and the like. As the alkyl-substituted mercaptan, an alkyl-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkyl-substituted mercaptan having 1 to 10 carbon atoms is more preferable. As the aryl group-substituted mercaptan, a phenyl group-substituted mercaptan is preferred. As the alkoxy-substituted mercaptan, an alkoxy-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkoxy-substituted mercaptan having 1 to 10 carbon atoms is more preferable. The acid group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having a carboxyl group and having 1 to 10 carbon atoms or an aryl group-substituted mercaptan having a carboxyl group and having 1 to 12 carbon atoms.

(Glass transition temperature of elastic body)
The glass transition temperature of the elastic body is preferably 80° C. or lower, more preferably 70° C. or lower, more preferably 60° C. or lower, more preferably 50° C. or lower, more preferably 40° C. or lower, more preferably 30° C. or lower. ° C. or lower is more preferred, 10 ° C. or lower is more preferred, 0 ° C. or lower is more preferred, -20 ° C. or lower is more preferred, -40 ° C. or lower is more preferred, -45 ° C. or lower is more preferred, and -50 ° C. or lower is more preferred. preferably -55°C or lower, more preferably -60°C or lower, more preferably -65°C or lower, more preferably -70°C or lower, more preferably -75°C or lower, more preferably -80°C or lower, -85°C or lower is more preferred, -90°C or lower is more preferred, -95°C or lower is more preferred, -100°C or lower is more preferred, -105°C or lower is more preferred, -110°C or lower is more preferred, -115 °C or lower is more preferred, -120°C or lower is even more preferred, and -125°C or lower is particularly preferred. In this specification, "glass transition temperature" may be referred to as "Tg". According to this configuration, polymer fine particles (A) having a low Tg and a resin composition having a low Tg can be obtained. As a result, the obtained resin composition can provide a cured product having excellent toughness. Moreover, according to the said structure, the viscosity of the resin composition obtained can be made lower. The Tg of the elastic body can be obtained by performing viscoelasticity measurement using a flat plate made of polymer fine particles (A). Specifically, Tg can be measured as follows: (1) For a flat plate made of polymer fine particles (A), a dynamic viscoelasticity measuring device (eg, DVA-200 manufactured by IT Keisoku Co., Ltd.) ) is used to perform dynamic viscoelasticity measurement under tensile conditions to obtain a tan δ graph; (2) Regarding the obtained tan δ graph, the tan δ peak temperature is taken as the glass transition temperature. Here, in the graph of tan δ, when a plurality of peaks are obtained, the lowest peak temperature is taken as the glass transition temperature of the elastic body.

On the other hand, the elastic modulus (rigidity) of the resulting cured product can be suppressed from decreasing, that is, a cured product having a sufficient elastic modulus (rigidity) can be obtained. 20° C. or higher is more preferred, 50° C. or higher is even more preferred, 80° C. or higher is particularly preferred, and 120° C. or higher is most preferred.

The Tg of the elastic body can be determined by the composition of the constituent units contained in the elastic body. In other words, the Tg of the resulting elastic body can be adjusted by changing the composition of the monomers used when manufacturing (polymerizing) the elastic body.

Here, when a homopolymer obtained by polymerizing only one type of monomer, a group of monomers that provide a homopolymer having a Tg greater than 0 ° C. is referred to as a monomer group a. . A group of monomers that provide a homopolymer having a Tg of less than 0° C. when only one type of monomer is polymerized is referred to as a monomer group b. 50 to 100% by weight (more preferably 65 to 99% by weight) of structural units derived from at least one monomer selected from monomer group a, and at least selected from monomer group b An elastic body G is defined as an elastic body containing 0 to 50% by weight (more preferably 1 to 35% by weight) of structural units derived from one type of monomer. The elastic body G has a Tg greater than 0°C. Moreover, when the elastic body contains the elastic body G, the obtained resin composition can provide a cured product having sufficient rigidity.

Even when the Tg of the elastic body is higher than 0° C., it is preferable to introduce a crosslinked structure into the elastic body. Methods for introducing the crosslinked structure include the methods described above.

Examples of monomers that can be included in the monomer group a include, but are not limited to, styrene, unsubstituted vinyl aromatic compounds such as 2-vinylnaphthalene; vinyl-substituted compounds such as α-methylstyrene; Aromatic compounds; ring-alkylated vinyls such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene and 2,4,6-trimethylstyrene Aromatic compounds; Ring alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; Ring halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; 4-acetoxystyrene and the like ring-ester-substituted vinyl aromatic compounds; ring hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; vinyl halides such as vinyl chloride; , indene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and isopropyl methacrylate; aromatic methacrylates such as phenyl methacrylate; methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; methacrylic monomers including methacrylic acid derivatives; certain acrylic acid esters such as isobornyl acrylate and tert-butyl acrylate; acrylic monomers including acrylic acid derivatives such as acrylonitrile; Further, monomers that can be included in the monomer group a include acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentanyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1- Monomers such as adamantyl acrylate and 1-adamantyl methacrylate that can provide a homopolymer having a Tg of 120° C. or higher when converted to a homopolymer are included. These monomers a may be used alone or in combination of two or more.

Examples of the monomer b include ethyl acrylate, butyl acrylate (also known as butyl acrylate), 2-ethylhexyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and the like. is mentioned. These monomers b may be used alone or in combination of two or more. Among these monomers b, particularly preferred are ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

(Volume average particle size of elastic body)
The volume average particle diameter of the elastic body is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, more preferably 0.08 μm to 2.00 μm, and further preferably 0.10 μm to 1.00 μm. It is preferably 0.10 μm to 0.80 μm, and particularly preferably 0.10 μm to 0.50 μm. When the volume average particle diameter of the elastic body is (a) 0.03 μm or more, an elastic body having a desired volume average particle diameter can be stably obtained. The heat resistance and impact resistance of the cured product or molded product to be obtained are improved. The volume average particle size of the elastic body can be measured by using an aqueous latex containing the elastic body as a sample and using a dynamic light scattering particle size distribution analyzer or the like. A method for measuring the volume average particle size of the elastic body will be described in detail in Examples below.

(Proportion of elastic body)
The proportion of the elastic body in the polymer fine particles (A) is preferably 40 to 97 wt%, more preferably 60 to 95 wt%, and 70 to 93 wt%, based on 100 wt% of the polymer fine particles (A) as a whole. is more preferred. When the proportion of the elastic body is (a) 40% by weight or more, the obtained resin composition can provide a cured product having excellent toughness and impact resistance, and (b) is 97% by weight or less. In this case, since the polymer fine particles (A) do not easily aggregate, the resin composition does not become highly viscous, and as a result, the obtained resin composition can be excellent in handling.

(Gel content of elastic body)
Preferably, the elastomer is swellable in a suitable solvent, but substantially insoluble. The elastic body is preferably insoluble in the thermosetting resin used.

The elastic body preferably has a gel content of 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more. When the gel content of the elastic body is within the above range, the obtained resin composition can provide a cured product having excellent toughness.

In the present specification, the method for calculating the gel content is as follows. First, an aqueous latex containing the polymer microparticles (A) is obtained, and then powder particles of the polymer microparticles (A) are obtained from the aqueous latex. The method for obtaining powdery particles of the polymer fine particles (A) from the aqueous latex is not particularly limited. For example, (a) the polymer fine particles (A) in the aqueous latex are aggregated, A method of dehydrating the substance and (c) further drying the agglomerate to obtain powdery particles of the polymer fine particles (A) can be mentioned. Next, 2.0 g of powder particles of polymer fine particles (A) are dissolved in 50 mL of methyl ethyl ketone (MEK). After that, the obtained MEK melt is separated into a component soluble in MEK (MEK soluble matter) and a component insoluble in MEK (MEK insoluble matter). Specifically, using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E), the obtained MEK lysate was subjected to centrifugation for 1 hour at a rotation speed of 30,000 rpm, and the lysate was Separation into MEK soluble matter and MEK insoluble matter. Here, a total of 3 sets of centrifugation operations are carried out. The weights of the obtained MEK soluble matter and MEK insoluble matter are measured, and the gel content is calculated from the following formula.
Gel content (%) = (weight of insoluble portion in methyl ethyl ketone)/{(weight of insoluble portion in methyl ethyl ketone) + (weight of soluble portion in methyl ethyl ketone)} x 100
(Modified example of elastic body)
In one embodiment of the present invention, the "elastic body" of the fine polymer particles (A) may consist of only one type of elastic body having the same composition of structural units. In this case, the "elastic body" of the fine polymer particles (A) is one selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers.

In one embodiment of the present invention, the "elastic body" of the fine polymer particles (A) may consist of a plurality of types of elastic bodies each having a different composition of structural units. In this case, the "elastic body" of the fine polymer particles (A) may be two or more selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers. In this case, the "elastic body" of the fine polymer particles (A) may be one selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers. In other words, the "elastic body" of the fine polymer particles (A) may be a plurality of types of diene-based rubbers, (meth)acrylate-based rubbers, or organosiloxane-based rubbers each having a different composition of structural units.

In one embodiment of the present invention, the case where the "elastic body" of the fine polymer particles (A) is composed of a plurality of types of elastic bodies having different compositions of structural units will be described. In this case, each of the plurality of types of elastic bodies is defined as elastic body ₁ , elastic body ₂ , . . . , and elastic body _n . Here, n is an integer of 2 or more. The "elastic body" of the fine polymer particles (A) may include a composite of separately polymerized elastic bodies ₁ , ₂ , . . . , and elastic body _n . The "elastic body" of the fine polymer particles (A) may include one elastic body obtained by polymerizing the elastic body ₁ , the elastic body ₂ , . . . and the elastic body _n in order. Such polymerization of a plurality of elastic bodies (polymers) in order is also called multistage polymerization. A single elastic body obtained by multi-stage polymerization of a plurality of types of elastic bodies is also referred to as a multi-stage polymerized elastic body. A method for producing the multi-stage polymer elastic body will be described in detail later.

A multistage polymerized elastic body composed of elastic body ₁ , elastic body ₂ , . . . , and elastic body _n will be described. In the multi-stage polymer elastic body, the elastic body _n may cover at least a portion of the elastic body n _{- 1, or may cover the entirety of the elastic body n-1} . In the multi-stage polymerized elastic body, part of the elastic body _n may be inside the elastic body _n-1 .

In the multi-stage polymer elastic body, each of the plurality of elastic bodies may form a layered structure. For example, when the multi-stage polymerized elastic body is composed of elastic body ₁ , elastic body ₂ , and elastic body ₃ , the elastic body ₁ forms the innermost layer, the elastic body ₂ layer is formed on the outer side of the elastic body ₁ , and A mode in which the layer of the elastic body ₃ is formed as the outermost layer of the elastic body outside the layer of the elastic body ₂ is also one mode of the present invention. Thus, a multi-stage polymerized elastic body in which each of a plurality of elastic bodies forms a layered structure can also be called a multi-layered elastic body. That is, in one embodiment of the present invention, the “elastic body” of the fine polymer particles (A) is (a) a composite of multiple types of elastic bodies, (b) a multi-stage polymerized elastic body and/or (c) a multi-layered elastic It may contain a body.

(Surface cross-linked polymer)
The rubber-containing graft copolymer preferably further has a surface-crosslinked polymer in addition to the elastic body and the graft portion graft-bonded to the elastic body. In other words, the fine polymer particles (A) preferably further have a surface-crosslinked polymer in addition to the elastic body and the graft portion graft-bonded to the elastic body. An embodiment of the present invention will be described below, taking as an example the case where the polymer fine particles (A) (for example, a rubber-containing graft copolymer) further has a surface-crosslinked polymer. In this case, (a) blocking resistance can be improved in the production of the fine polymer particles (A), and (b) dispersibility of the fine polymer particles (A) in the thermosetting resin is improved. These reasons are not particularly limited, but can be presumed as follows: By covering at least a part of the elastic body with the surface cross-linked polymer, the exposure of the elastic part of the fine polymer particles (A) is reduced. As a result, the elastic bodies are less likely to stick to each other, thereby improving the dispersibility of the fine polymer particles (A).

When the polymer microparticles (A) have a surface-crosslinked polymer, the following effects can also be obtained: (a) the effect of reducing the viscosity of the resin composition, (b) the effect of increasing the crosslink density in the elastic body, and (c) The effect of increasing the graft efficiency of the graft portion. The crosslink density in the elastic means the degree of the number of crosslink structures in the whole elastic.

The surface-crosslinked polymer contains, as structural units, 30 to 100% by weight of structural units derived from a polyfunctional monomer and 0 to 70% by weight of structural units derived from other vinyl monomers, a total of 100 % by weight of the polymer.

Polyfunctional monomers that can be used to polymerize the surface-crosslinked polymer include the same polyfunctional monomers as described above. Among these polyfunctional monomers, polyfunctional monomers that can be preferably used for polymerization of the surface-crosslinked polymer include allyl methacrylate, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate (e.g. 1,3-butylene glycol dimethacrylate), butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates. Only one type of these polyfunctional monomers may be used, or two or more types may be used in combination.

The polymer microparticles (A) may contain a surface-crosslinked polymer polymerized independently of the polymerization of the rubber-containing graft copolymer, or may contain a surface-crosslinked polymer polymerized together with the rubber-containing graft copolymer. May include coalescing. The fine polymer particles (A) may be a multi-stage polymer obtained by multi-stage polymerization of an elastic body, a surface-crosslinked polymer and a graft portion in this order. In any of these embodiments, the surface-crosslinked polymer can cover at least a portion of the elastic body.

Surface cross-linked polymers can also be considered part of the elastomer. In other words, the surface-crosslinked polymer can also be regarded as a part of the rubber-containing graft copolymer, and can also be said to be a surface-crosslinked polymer portion. When the polymer microparticles (A) contain a surface-crosslinked polymer, the graft portion may be (a) graft-bonded to an elastic body other than the surface-crosslinked polymer, and (b) to the surface-crosslinked polymer. (c) may be graft-bonded to both the elastic body other than the surface-crosslinked polymer and the surface-crosslinked polymer. When the polymer fine particles (A) contain a surface-crosslinked polymer, the volume-average particle diameter of the elastic body mentioned above means the volume-average particle diameter of the elastic body containing the surface-crosslinked polymer.

A case (Case D) in which the fine polymer particles (A) are a multi-stage polymer obtained by multi-stage polymerization of an elastic body, a surface-crosslinked polymer and a graft portion in this order will be described. In Case D, the surface cross-linked polymer may cover a portion of the elastic or may cover the entire elastic. In case D, part of the surface-crosslinked polymer may be embedded inside the elastic body. In Case D, the graft portion may cover a portion of the surface cross-linked polymer or may cover the entire surface cross-linked polymer. In Case D, part of the graft portion may be embedded inside the surface-crosslinked polymer. In Case D, the elastic body, the surface-crosslinked polymer and the graft portion may have a layered structure. For example, the elastic body is the innermost layer (core layer), the surface-crosslinked polymer layer is present as an intermediate layer outside the elastic body, and the graft portion layer is the outermost layer (shell layer) outside the surface-crosslinked polymer. The present aspect is also an aspect of the invention.

(Volume average particle diameter (Mv) of polymer microparticles (A))
The volume average particle diameter (Mv) of the fine polymer particles (A) is preferably from 0.03 μm to 50.00 μm, since a highly stable resin composition having a desired viscosity can be obtained. 05 μm to 10.00 μm is more preferable, 0.08 μm to 2.00 μm is more preferable, 0.10 μm to 1.00 μm is still more preferable, 0.10 μm to 0.80 μm is even more preferable, and 0.10 μm to 0.50 μm is particularly preferred. When the volume average particle diameter (Mv) of the polymer fine particles (A) is within the above range, the advantage is that the polymer fine particles (A) have good dispersibility in the resin (B) (for example, thermosetting resin). also have In the present specification, the "volume average particle diameter (Mv) of the polymer microparticles (A)" is intended to be the volume average particle diameter of the primary particles of the polymer microparticles (A), unless otherwise specified. do. The volume average particle size of the polymer fine particles (A) can be measured using a dynamic light scattering particle size distribution analyzer or the like using an aqueous latex containing the polymer fine particles (A) as a sample.

(2-2. Method for producing polymer microparticles (A))
Hereinafter, a case in which the polymer fine particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body will be taken as an example, and the polymer fine particles (A ) will be described below. The fine polymer particles (A) can be produced, for example, by polymerizing an elastic body and then graft-polymerizing a polymer forming a graft portion to the elastic body in the presence of the elastic body.

Polymer microparticles (A) can be produced by known methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. Specifically, the polymerization of the elastic body, the polymerization of the graft portion (graft polymerization), and the polymerization of the surface-crosslinked polymer in the fine polymer particles (A) are performed by known methods such as emulsion polymerization, suspension polymerization, It can be carried out by a method such as a microsuspension polymerization method. Among these, the emulsion polymerization method is particularly preferable as the method for producing the polymer fine particles (A). The emulsion polymerization method has the advantages of (a) facilitating compositional design of the polymer microparticles (A) and (b) facilitating industrial production of the polymer microparticles (A). Hereinafter, the method for producing the elastic body, the graft portion, and the surface-crosslinked polymer having any configuration that can be contained in the fine polymer particles (A) will be described.

(Manufacturing method of elastic body)
Consider the case where the elastic body contains at least one selected from the group consisting of diene-based rubbers and (meth)acrylate-based rubbers. In this case, the elastic body can be produced, for example, by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization. .

Consider the case where the elastic body contains an organosiloxane rubber. In this case, the elastic body can be produced, for example, by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization. .

A case where the "elastic body" of the fine polymer particles (A) consists of a plurality of types of elastic bodies (eg, elastic body ₁ , elastic body ₂ , . . . , elastic body _n ) will be described. In this case, the elastic _{bodies 1 1} , _{2 2} , . may be produced. _{Alternatively} , elastic body _{1 1} , elastic body _{2 2} , .

A specific description will be given of the multi-stage polymerization of the elastic body. For example, a multi-stage polymerized elastic body can be obtained by sequentially performing the following steps (1) to (4): (1) elastic body ₁ is polymerized to obtain elastic body ₁ ; ( _{3) Polymerize elastic 3 in} the presence of elastic _{1 + 2} to obtain three-step elastic ₁₊₂₊₃ ; ( 4) Thereafter, following the same procedure, the elastic body _n is polymerized in the presence of the elastic body _{1+2+...+(n-1)} to obtain the multi-stage polymerized elastic body _1+2+...+n .

(Manufacturing method of graft portion)
The graft portion can be formed, for example, by polymerizing a monomer used for forming the graft portion by known radical polymerization in the presence of an arbitrary polymer (for example, an elastic body). When (a) the elastic body or (b) the polymer fine particle precursor containing the elastic body and the surface-crosslinked polymer is obtained as an aqueous latex, the polymerization of the graft portion is preferably carried out by an emulsion polymerization method. The graft portion can be manufactured, for example, according to the method described in WO2005/028546.

A method of manufacturing a graft portion when the graft portion is composed of a plurality of types of graft portions (for example, graft portion _{1 1} , graft portion _{2 2} , . . . , graft portion _n 2 ) will be described. In this case, the graft portion _{1 1} , the _graft portion _{2 2} , . (composite) may be produced. Alternatively, the _graft portion _{1 1} , the graft portion _{2 2} , .

The multi-stage polymerization of the graft portion will be specifically described. For example, a multi-stage polymerized graft portion can be obtained by sequentially performing the steps (1) to (4) below: (1) Graft portion ₁ is polymerized to obtain graft portion ₁ ; ( _{3) then polymerize graft portion 3 in} the presence of graft portion _{1 + 2} to obtain three-step graft portion ₁₊₂₊₃ ; ( 4) Thereafter, after performing the same procedure, the graft portion _n is polymerized in the presence of the graft portion 1 _{+ 2+} .

When the graft portion is composed of a plurality of types of graft portions, the polymer microparticles (A) may be produced by polymerizing the graft portions having a plurality of types of graft portions and then graft-polymerizing the graft portions onto the elastic body. . The polymer microparticles (A) may be produced by sequentially carrying out multistage graft polymerization of a plurality of types of polymers constituting the graft portion to the elastic body in the presence of the elastic body.

(Method for producing surface-crosslinked polymer)
A surface-crosslinked polymer can be formed by polymerizing a monomer used for forming the surface-crosslinked polymer by known radical polymerization in the presence of an arbitrary polymer (for example, an elastic body). When the elastic body is obtained as an aqueous latex, the polymerization of the surface-crosslinked polymer is preferably carried out by an emulsion polymerization method.

When an emulsion polymerization method is employed as the method for producing the polymer fine particles (A), a known emulsifier (dispersant) can be used as an emulsifier (dispersant) in the production of the polymer fine particles (A).

Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, and polyacrylic acid derivatives. Examples of anionic emulsifiers include sulfur-based emulsifiers, phosphorus-based emulsifiers, sarcosic acid-based emulsifiers, and carboxylic acid-based emulsifiers. Examples of sulfur-based emulsifiers include sodium dodecylbenzenesulfonate (abbreviation: SDBS). Phosphorus-based emulsifiers include sodium polyoxyethylene lauryl ether phosphate and the like.

When an emulsion polymerization method is employed as the method for producing the polymer fine particles (A), a thermal decomposition initiator can be used for the production of the polymer fine particles (A). The thermal decomposition initiators include, for example, (a) 2,2′-azobisisobutyronitrile and (b) peroxides such as organic peroxides and inorganic peroxides. agents can be mentioned. Examples of the organic peroxides include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t- and hexyl peroxide. Examples of the inorganic peroxides include hydrogen peroxide, potassium persulfate, and ammonium persulfate.

A redox initiator can also be used for the production of the polymer microparticles (A). The redox initiator includes (a) peroxides such as organic peroxides and inorganic peroxides, and (b) transition metal salts such as iron (II) sulfate, sodium formaldehyde sulfoxylate, glucose and the like. It is an initiator used in combination with a reducing agent. Furthermore, if necessary, a chelating agent such as disodium ethylenediaminetetraacetate and, if necessary, a phosphorus-containing compound such as sodium pyrophosphate may be used in combination.

When a redox initiator is used, polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set in a wide range. Therefore, it is preferable to use a redox initiator. Among redox initiators, redox initiators using organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramenthane hydroperoxide, and t-butyl hydroperoxide as peroxides are preferred. The amount of the initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when a redox initiator is used, can be used within a known range.

For the purpose of introducing a crosslinked structure into the elastic body, the graft part or the surface crosslinked polymer, when using a polyfunctional monomer in the polymerization of the elastic body, the graft part or the surface crosslinked polymer, a known chain transfer agent is used. can be used within the range of the amount used. By using a chain transfer agent, the molecular weight and/or the degree of cross-linking of the resulting elastomer, graft portion or surface-crosslinked polymer can be easily adjusted.

In addition to the components described above, a surfactant can be used for the production of the polymer microparticles (A). The types and amounts of the surfactants used are within known ranges.

In the production of the polymer microparticles (A), conditions within known numerical ranges can be appropriately applied to the polymerization conditions such as polymerization temperature, pressure, and deoxidization.

(2-3. Resin (B))
The resin (B) is not particularly limited, but may be a thermosetting resin, a thermoplastic resin, or any combination of a thermosetting resin and a thermoplastic resin.

(Thermosetting resin)
The thermosetting resin is at least one selected from the group consisting of resins containing polymers obtained by polymerizing ethylenically unsaturated monomers, epoxy resins, phenol resins, polyol resins and amino-formaldehyde resins (melamine resins). It preferably contains a thermosetting resin of some kind, more preferably an epoxy resin. The resin (B) contains at least one thermosetting resin selected from the above group, so that (a) the resulting resin composition can provide a cured product or molded article having excellent heat resistance, and ( b) It has the advantage of being able to improve the dispersibility of the polymer fine particles (A) in the resin composition.

Thermosetting resins also include resins containing polymers obtained by polymerizing aromatic polyester raw materials. Examples of aromatic polyester raw materials include aromatic vinyl compounds, (meth)acrylic acid derivatives, vinyl cyanide compounds, radically polymerizable monomers such as maleimide compounds, dimethyl terephthalate, and alkylene glycol. These thermosetting resins may be used alone or in combination of two or more.

(Ethylenically unsaturated monomer)
The ethylenically unsaturated monomer is not particularly limited as long as it has at least one ethylenically unsaturated bond in the molecule.

Examples of ethylenically unsaturated monomers include acrylic acid, α-alkyl acrylic acid, α-alkyl acrylic acid ester, β-alkyl acrylic acid, β-alkyl acrylic acid ester, methacrylic acid, esters of acrylic acid, and methacrylic acid. Esters, vinyl acetates, vinyl esters, unsaturated esters, polyunsaturated carboxylic acids, polyunsaturated esters, maleic acid, maleic esters, maleic anhydride and acetoxystyrene. These may be used alone or in combination of two or more.

(Epoxy resin)
The epoxy resin is not particularly limited as long as it has at least one epoxy bond in the molecule.

Specific examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, novolac type epoxy resin, Glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A (or F) type epoxy resin, fluorinated epoxy resin, rubber-modified epoxy resin containing polybutadiene or NBR, glycidyl ether of tetrabromobisphenol A, etc. Flame-retardant epoxy resins, p-oxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol type epoxy resins, diaminodiphenylmethane type epoxy resins, urethane-modified epoxy resins having urethane bonds, various alicyclic epoxy resins, polyhydric Glycidyl ethers of alcohols, hydantoin type epoxy resins, epoxidized unsaturated polymers such as petroleum resins, aminoglycidyl ether resins, and the like. Examples of the polyhydric alcohol include N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, and glycerin. Epoxy resins also include epoxy compounds obtained by subjecting the above-mentioned epoxy resins to addition reaction with bisphenol A (or F) or polybasic acids. Epoxy resins are not limited to these, and commonly used epoxy resins can be used. These epoxy resins may be used alone or in combination of two or more.

Among the epoxy resins described above, those having at least two epoxy groups in one molecule have high reactivity in curing the resin composition, and the resulting cured product tends to form a three-dimensional network. preferable. Among epoxy resins having at least two epoxy groups in one molecule, epoxy resins containing bisphenol-type epoxy resins as a main component are preferred because of their excellent economic efficiency and availability.

(Phenolic resin)
The phenol resin is not particularly limited as long as it is a compound obtained by reacting phenols and aldehydes. Examples of phenols include, but are not limited to, phenol, ortho-cresol, meta-cresol, para-cresol, xylenol, para-tert-butylphenol, para-octylphenol, para-phenylphenol, bisphenol A, bisphenol F, and resorcinol. be done. Particularly preferred phenols include phenol and cresol.

Aldehydes include, but are not limited to, formaldehyde, acetaldehyde, butyraldehyde, acrolein, and mixtures thereof. As the aldehydes, it is possible to use the above-mentioned aldehyde-generating source substances or solutions of these aldehydes. As the aldehyde, formaldehyde is preferred because it is easy to operate when reacting phenols and aldehydes.

The molar ratio (F/P) of phenols (P) and aldehydes (F) (hereinafter also referred to as reaction molar ratio) when reacting phenols and aldehydes is not particularly limited. When an acid catalyst is used in the reaction, the reaction molar ratio (F/P) is preferably 0.4-1.0, more preferably 0.5-0.8. When an alkali catalyst is used in the reaction, the reaction molar ratio (F/P) is preferably 0.4-4.0, more preferably 0.8-2.5. When the reaction molar ratio is at least the above lower limit, the yield is not too low, and there is no possibility that the molecular weight of the obtained phenol resin will be small. On the other hand, when the reaction molar ratio is equal to or less than the above upper limit, the molecular weight of the phenol resin does not become too large and the softening point does not become too high, so sufficient fluidity can be obtained during heating. Moreover, when the reaction molar ratio is equal to or less than the upper limit, the molecular weight can be easily controlled, and there is no risk of gelation or partial gelation due to reaction conditions.

(Polyol resin)
A polyol resin is a compound having two or more active hydrogens at its terminals, and is a bifunctional or higher polyol having a molecular weight of about 50 to 20,000. Examples of polyol resins include aliphatic alcohols, aromatic alcohols, polyether-type polyols, polyester-type polyols, polyolefin polyols, and acrylic polyols.

Fatty alcohols may be either dihydric alcohols or trihydric or higher alcohols (trihydric alcohols, tetrahydric alcohols, etc.). Dihydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl -Alkylene glycols such as 1,5-pentanediol and neopentyl glycol (especially alkylene glycols having about 1 to 6 carbon atoms), dehydration of two or more molecules (for example, about 2 to 6 molecules) of the alkylene glycols condensates (diethylene glycol, dipropylene glycol, tripropylene glycol, etc.); Examples of trihydric alcohols include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol (especially trihydric alcohols having about 3 to 10 carbon atoms). Examples of tetrahydric alcohols include pentaerythritol and diglycerin. Moreover, saccharides, such as a monosaccharide, an oligosaccharide, and a polysaccharide, are mentioned.

Examples of aromatic alcohols include bisphenols such as bisphenol A and bisphenol F; biphenyls such as dihydroxybiphenyl; polyhydric phenols such as hydroquinone and phenol-formaldehyde condensates; and naphthalene diol.

Examples of polyether-type polyols include random copolymers obtained by ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. in the presence of one or more initiators containing active hydrogen. Coalescing or block copolymers and the like, and mixtures of these copolymers and the like. Active hydrogen-containing initiators used for ring-opening polymerization of polyether-type polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1, Diols such as 6-hexanediol, neopentyl glycol and bisphenol A; Triols such as trimethylolethane, trimethylolpropane and glycerin; Sugars such as monosaccharides, oligosaccharides and polysaccharides; Sorbitol; Ammonia, ethylenediamine, urea, monomethyl amines such as diethanolamine and monoethyldiethanolamine;

Examples of polyester-type polyols include (a) polybasic acids such as maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, dodecanedioic acid, isophthalic acid, and azelaic acid and/or their acid anhydrides, and (b ) a polyhydric alcohol such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, A polymer obtained by polycondensation at a temperature of 150 to 270° C. in the presence of an esterification catalyst may be mentioned. Furthermore, (a) polyester-type polyols include ring-opening polymers such as ε-caprolactone and valerolactone, and (b) active hydrogen compounds having two or more active hydrogens such as polycarbonate diols and castor oil. be done.

Polyolefin-type polyols include polybutadiene polyol, polyisoprene polyol, hydrogenated products thereof, and the like.

Examples of acrylic polyols include (a) hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, and vinylphenol, and (b) n-butyl (meth)acrylate and 2-ethylhexyl Examples include copolymers with general-purpose monomers such as (meth)acrylates, and mixtures of these copolymers.

Among these polyol resins, polyether-type polyols are preferred because the obtained resin composition has a low viscosity and excellent workability, and the resin composition can provide a cured product having an excellent balance between hardness and toughness. Moreover, among these polyol resins, polyester-type polyols are preferable because the obtained resin composition can provide a cured product having excellent adhesiveness.

(amino-formaldehyde resin)
The amino-formaldehyde resin is not particularly limited as long as it is a compound obtained by reacting an amino compound with an aldehyde in the presence of an alkaline catalyst. Examples of the amino compounds include melamine; 6-substituted guanamines such as guanamine, acetoguanamine and benzoguanamine; CTU guanamine (3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl) ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane), CMTU guanamine (3,9-bis[(3,5-diamino-2,4,6-triazaphenyl)methyl]- amine-substituted triazine compounds such as 2,4,8,10-tetraoxaspiro[5,5]undecane); and ureas such as urea, thiourea, and ethyleneurea. Examples of the amino compound include substituted melamine compounds in which the hydrogen of the amino group of melamine is substituted with an alkyl group, an alkenyl group, and/or a phenyl group (U.S. Pat. No. 5,998,573 (corresponding Japanese publication: JP-A-9-143238), and substituted melamine compounds in which the hydrogen of the amino group of melamine is substituted with a hydroxyalkyl group, a hydroxyalkyloxyalkyl group, and/or an aminoalkyl group (US Pat. No. 5). , 322,915 (corresponding to Japanese Laid-Open Publication No. 5-202157)) can also be used. As the amino compound, among the above-mentioned compounds, melamine, guanamine, acetoguanamine, and benzoguanamine, which are polyfunctional amino compounds, are preferable because they are industrially produced and inexpensive, and melamine is particularly preferable. The above amino compounds may be used alone or in combination of two or more. In addition to these amino compounds, (a) phenols such as phenol, cresol, alkylphenol, resorcinol, hydroquinone and pyrogallol, and (b) aniline may be additionally used.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and furfural. As the aldehydes, formaldehyde and paraformaldehyde are preferable because they are inexpensive and have good reactivity with the above-mentioned amino compounds. In the production of amino-formaldehyde resin, aldehydes are preferably used in an amount of 1.1 to 6.0 mol, preferably 1.2 to 4.0 mol, per effective aldehyde group per 1 mol of the amino compound. is particularly preferred.

(Thermoplastic resin)
As the thermoplastic resin, for example, the structural unit is derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers. Examples thereof include polymers containing structural units. Thermoplastic resins in resin (B) also include polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes and polyvinyl acetates. In the resin (B), only one type of thermoplastic resin may be used, or two or more types may be used in combination.

(others)
Fats and fatty acid esters are also included in resin (B) herein. Examples of fats and oils that can be suitably used as the resin (B) include epoxidized fats and oils such as epoxidized soybean oil and epoxidized linseed oil. As the epoxidized soybean oil, a commercial product can be used, and examples thereof include Adekaiser O-130P manufactured by ADEKA. Fatty acid esters that can be preferably used as the resin (B) include epoxidized fatty acid esters such as epoxidized fatty acid butyl, epoxidized fatty acid 2-ethylhexyl, epoxidized fatty acid octyl ester and epoxidized fatty acid alkyl ester.

Epoxidized oils and fats and epoxidized fatty acid esters are sometimes referred to as epoxy plasticizers. That is, in this specification, the epoxy plasticizer is also included in the resin (B). Epoxy plasticizers other than epoxidized fats and epoxidized fatty acid esters include diepoxystearyl epoxyhexahydrophthalate and di-2-ethylhexyl epoxyhexahydrophthalate.

Each of the thermosetting resins, thermoplastic resins, mixtures of thermosetting resins and thermoplastic resins, fats and oils, and fatty acid esters described above can be used in combination with antioxidants. In this specification, antioxidants are considered part of resin (B) only when used in admixture with each of the substances mentioned above. If only antioxidants are used, the antioxidants are not considered resin (B).

The antioxidant is not particularly limited. Examples of antioxidants include (a) primary antioxidants such as phenol antioxidants, amine antioxidants, lactone antioxidants, and hydroxylamine antioxidants, and (b) sulfur antioxidants. and secondary antioxidants such as phosphorus-based antioxidants.

A hindered phenolic antioxidant can be mentioned as said phenolic antioxidant. Hindered phenol-based antioxidants include compounds having a hindered phenol structure or a semi-hindered phenol structure in the molecule. As the phenol-based antioxidant, a commercially available product can be used, for example, Irganox 245 manufactured by BASF Japan Ltd. can be mentioned.

The amine-based antioxidant is not particularly limited, and conventionally known ones can be widely used. Specific examples of amine antioxidants include amine-ketone compounds such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4 - trimethylquinoline, and reaction products of diphenylamine and acetone, and the like.

The amine antioxidants also include aromatic amine compounds. Aromatic amine compounds include naphthylamine antioxidants, diphenylamine antioxidants, and p-phenylenediamine antioxidants.

Lactone-based antioxidants, hydroxylamine-based antioxidants, and sulfur-based antioxidants are not particularly limited, and conventionally known antioxidants can be widely used.

The phosphorus-based antioxidant is not particularly limited, and conventionally known ones can be widely used. Phosphoric acid and phosphate esters containing active hydrogen can adversely affect the storage stability of the obtained resin composition containing powder and the heat resistance of the cured product or molded product provided by the resin composition. Therefore, alkyl phosphites, aryl phosphites, alkylaryl phosphite compounds, etc., which do not contain phosphoric acid or phosphoric acid esters in their molecules, are preferable as phosphorus-based antioxidants.

Other conventionally known substances may be used as the antioxidant. Examples of antioxidants include "Antioxidant Handbook" published by Taiseisha (first edition published on October 25, 1976), and "Polymer Additives Handbook" published by CMC Publishing (edited by Toru Haruna, November 2010). 7, 1st Edition), etc. may be used.

Resin (B) is (a) a liquid having a viscosity of from 100 mPa·s to 1,000,000 mPa·s, or (b) a semi-solid, or (c) a solid at 25° C. is preferred.

When the resin (B) is liquid at 25°C, the viscosity of the resin (B) at 25°C is preferably 1,000,000 mPa s or less, more preferably 750,000 mPa s or less. preferably 700,000 mPa s or less, more preferably 500,000 mPa s or less, more preferably 350,000 mPa s or less, and 300,000 mPa s or less is more preferably 250,000 mPa s or less, more preferably 100,000 mPa s or less, more preferably 75,000 mPa s or less, and 50,000 mPa s or less. more preferably 30,000 mPa s or less, more preferably 25,000 mPa s or less, even more preferably 20,000 mPa s or less, 15,000 mPa s The following are particularly preferred. According to the above configuration, the resin composition has an advantage of excellent fluidity.

The viscosity of the resin (B) at 25° C. is preferably 100 mPa·s or more, more preferably 200 mPa·s or more, more preferably 300 mPa·s or more, and more preferably 400 mPa·s or more. It is more preferably 500 mPa s or more, more preferably 750 mPa s or more, even more preferably 1,000 mPa s or more, and 1,500 mPa s or more. is particularly preferred. According to this configuration, the resin (B) does not impregnate the polymer microparticles (A), but enters between the plurality of polymer microparticles (A) to prevent fusion between the polymer microparticles (A). can be done. Therefore, the resin (B) can prevent fusion between the fine polymer particles (A).

The viscosity of the resin (B) at 25° C. is more preferably 100 mPa·s to 750,000 mPa·s, more preferably 100 mPa·s to 700,000 mPa·s, and more preferably 100 mPa·s to 350,000 mPa·s. , More preferably 100 mPa s to 300,000 mPa s, more preferably 100 mPa s to 50,000 mPa s, still more preferably 100 mPa s to 30,000 mPa s, 100 mPa s to 15,000 mPa s Especially preferred.

If resin (B) is semi-solid at 25°C, resin (B) is also said to be semi-liquid at 25°C, and resin (B) has a viscosity of greater than 1,000,000 mPa·s at 25°C. It can be said that it does. When the resin (B) is (a) semi-solid or (b) solid at 25° C., the resin composition has the advantage of being less sticky and easier to handle.

In this specification, the viscosities of the resin (B), the resin composition, the aqueous liquid, and the mixture are the values obtained by measuring with a viscometer (for example, digital viscometer DV-II+Pro type manufactured by BROOKFIELD). do.

The resin (B) preferably has an endothermic peak of 25° C. or lower, more preferably 0° C. or lower, in a thermogram of differential scanning calorimetry (DSC). According to the above configuration, the resin (B) has an advantage of excellent fluidity.

In this separation method, the resin (B) preferably contains an epoxy resin. According to this configuration, (a) the obtained resin composition can provide a cured product or molded product having excellent heat resistance, and (b) the dispersibility of the polymer fine particles (A) in the resin composition can be improved. have the advantage of being able to

(2-4. Mixture of resin composition and aqueous liquid)
The mixture separated by this separation method is a mixture of the resin composition containing the polymer microparticles (A) and the resin (B) and the aqueous liquid, and includes the resin composition containing lumps of the aqueous liquid.

The viscosity of the mixture at 25° C. is preferably 100 mPa·s or more, more preferably 500 mPa·s or more, and even more preferably 1,000 mPa·s or more. Mixtures having viscosities in the above ranges have conventionally had the problem of being difficult to separate stably, but in the present separation method, they exhibit rather favorable behavior and efficiently separate the resin composition and the aqueous liquid. It has the advantage that it can be separated. In other words, this separation method is particularly suitable for separating a mixture having a viscosity within the above range.

The upper limit of the viscosity of the mixture is not particularly limited. s or less, more preferably 500,000 mPa s or less, more preferably 100,000 mPa s or less, more preferably 60,000 mPa s or less, 50,000 mPa ·s or less, more preferably 30,000 mPa·s or less, and particularly preferably 15,000 mPa·s or less.

The viscosity of the mixture can be adjusted within a desired range by appropriately adjusting the viscosities of the resin composition and the aqueous liquid in the mixture and the mixing ratio of these.

The mixture may be viscous. The viscosity of the mixture is not particularly limited. This separation method has the advantage that the resin composition and the water-based liquid can be separated even if the mixture has a certain viscosity. In other words, this separation method can also be suitably used when separating a mixture having a certain viscosity.

When the weight of the mixture is 100% by weight, the water content of the mixture may be, for example, 1% to 90% by weight, more preferably 1% to 70% by weight, and 1% by weight. More preferably ~50% by weight, particularly preferably 1% to 30% by weight. In a highly viscous mixture having a water content of 90% by weight or less, the water-based liquid may exist as a mass entrained in the resin composition. It has been difficult with the prior art to separate the aqueous liquid from the mixture in such a state. The lower the water content of the mixture, the higher the viscosity of the mixture, and the greater the difference between the viscosity of the resin composition in the mixture and the viscosity of the aqueous liquid. As a result, the water-based liquid tends to get caught in the resin composition, and it is difficult to remove (separate) the water-based liquid caught in the resin composition to further reduce the water content. However, this separation method has the advantage that it can be preferably carried out when the water content of the mixture is relatively low, and the resin composition and the aqueous liquid can be efficiently separated. In other words, this separation method is particularly suitable for separating a mixture having a water content within the above range.

When the water content of the mixture is higher than, for example, 90% by weight, a dehydration step is carried out to remove part of the aqueous liquid so that the water content of the mixture is 90% by weight or less before subjecting the mixture to the defoaming step. may A dehydration method for removing part of the aqueous liquid in the mixture will be described in detail in the section (2-6. Dehydration step) below.

(2-5. Mixture preparation method)
Next, a method for preparing a mixture, which is an object to be subjected to this separation method, will be described. The method of preparing the mixture is not particularly limited, and various methods can be used. For example, a mixture can be prepared by mixing the resin composition and water. The method for preparing the resin composition used in the preparation method is not particularly limited, and examples thereof include the following methods (a1) to (a3):
(a1) A method of mixing fine particles of polymer fine particles (A) and resin (B) to obtain a resin composition containing polymer fine particles (A) and resin (B);
(a2) Using an aqueous latex of fine polymer particles (A), a coagulate of fine polymer particles (A) is obtained. A method of mixing the resulting coagulate of polymer fine particles (A) with resin (B) to obtain a resin composition containing polymer fine particles (A) and resin (B); and (a3) polymer fine particles A method of mixing a resin mixture (D) containing (A) and resin (C) with resin (B) to obtain a resin composition containing polymer fine particles (A) and resin (B).

The method for producing the powdery particles of the polymer fine particles (A) used in (a1) is not particularly limited, and any known method can be used.

The aqueous latex of the fine polymer particles (A) used in (a2) is obtained by emulsion polymerization of the fine polymer particles (A).

In (a2), the method for obtaining the coagulate of the polymer fine particles (A) using the aqueous latex of the polymer fine particles (A) includes (a3-1) the aqueous latex of the polymer fine particles (A) and an organic and (a3-2) a method of adding a coagulant such as an inorganic salt to the aqueous latex of the fine polymer particles (A). Any known method can be used.

Examples of the resin (C) in (a3) include various resins described in the section (2-3. Resin (B)) above. The resin (C) may be the same resin as the resin (B), or may be a resin different from the resin (B). Examples of the method for producing the resin mixture (D) include the method for producing a resin composition described below.

The mixture may be prepared by method (a4) as follows:
(a4) A coagulant such as an inorganic salt is added to a resin mixture containing an aqueous latex of polymer fine particles (A) and a resin (B) to coagulate the polymer fine particles (A) and the resin (B) in the resin mixture. analyze. A method of obtaining a mixture containing a resin composition, which is a coagulate containing the polymer fine particles (A) and the resin (B), and an aqueous liquid by such coagulation;

The method for producing the resin mixture containing the aqueous latex of the polymer fine particles (A) and the resin (B) used in (a4) includes (a1-1) a resin ( B), a method of adding directly, a method of adding in the form of an aqueous emulsion, or a method of adding in the form of a solution, and (a1-2) adding resin (B) to aqueous latex of fine polymer particles (A) a method of directly adding, a method of adding in an aqueous emulsion state, or a method of adding in a solution state, (a1-3) a method of polymerizing the resin (B) in the presence of the polymer fine particles (A), etc., but not limited thereto, and any known method can be used.

A more specific embodiment of (a4) may include the following steps (b1) to (b4), but is not limited to such a production method: (b1) Polymer microparticles (A) (b2) a shearing step of applying a shear stress to the resin mixture obtained in the resin mixing step; (b3) the resin mixture obtained in the shearing step (b4) a mixing step of mixing the mixture obtained by the coagulant addition step;

(resin mixing process)
The resin mixing step is a step of mixing the polymer fine particles (A) with the resin (B). The resin mixing step can be said to be a step of adding the resin (B) to the polymer fine particles (A) to obtain a mixture, and can also be said to be a step of mixing the obtained mixture. The resin mixing step can also be said to be a step of mixing the fine polymer particles (A) and the resin (B).

In the resin mixing step, the polymer fine particles (A) may be (i) in the form of powder particles, or (ii) in a state of being dispersed in a solvent, i.e., containing the polymer fine particles (A). It may be in the form of an aqueous latex. The method for producing the aqueous latex containing polymer fine particles (A) is as described above.

Various methods can be used for adding the resin (B) to the polymer fine particles (A), and there is no particular limitation. Examples of the method include: (i) a method of directly adding the resin (B) to the polymer fine particles (A); and the like. The "solution in which the resin (B) is dissolved" can also be said to be an "emulsion in which the resin (B) is dispersed in water". An "emulsion" may also be referred to as an "emulsion" or "aqueous emulsion".

Also, the means for mixing the polymer fine particles (A) and the resin (B) is not particularly limited. For example, the polymer fine particles (A) and the resin (B) may be stirred, kneaded with a kneader, kneaded with an extruder, or mixed with a rotation/revolution mixer.

In the resin mixing step, the amount of the fine polymer particles (A) and the amount of the resin (B) are not particularly limited. In the resin mixing step, when the total of the polymer fine particles (A) and the resin (B) is 100% by weight, (i) 1 to 70% by weight of the polymer fine particles (A) and 30 to 70% by weight of the resin (B) (ii) mixing 1 to 65% by weight of polymer fine particles (A) and 35 to 99% by weight of resin (B). More preferably, (iii) 1 to 60% by weight of the polymer fine particles (A) and 40 to 99% by weight of the resin (B) are mixed, and (iv) the polymer fine particles (A) It is more preferable to include a step of mixing 1 to 55% by weight and 45 to 99% by weight of the resin (B), and (v) 1 to 50% by weight of the polymer fine particles (A) and 50% by weight of the resin (B). (vi) mixing 1 to 45% by weight of polymer fine particles (A) and 55 to 99% by weight of resin (B). (vii) It is particularly preferable to include a step of mixing 1 to 40% by weight of the fine polymer particles (A) and 60 to 99% by weight of the resin (B).

The amounts of polymer fine particles (A) and resin (B) added in the resin mixing step are the amounts of polymer fine particles (A) and resin (B) contained in the mixture to be measured in the concentration measurement step. Therefore, the amount of the polymer fine particles (A) and the resin (B) added in the resin mixing step depends on the concentration of the polymer fine particles (A) in the finally obtained resin composition and the concentration of the resin composition. It is preferable to adjust the physical properties and the like so as to achieve desired aspects.

(Shearing process)
The shearing step is a step of applying a shearing stress to the mixture obtained by the resin mixing step.

The method of applying shear stress to the mixture is not particularly limited, and various techniques can be used. Examples of the method include a method of stirring the mixture at 3,000 to 25,000 rpm with a homomixer, a method of stirring the mixture at 500 to 12,000 rpm with a high-shear emulsifier, and a method of stirring the mixture with a high-pressure homogenizer. , and so on.

When the viscosity of the resin (B) is high, it is preferable to adjust the viscosity of the resin (B) to an optimum viscosity. For example, the optimum viscosity of the resin (B) is preferably 100 mPa s to 750,000 mPa s, more preferably 150 mPa s to 700,000 mPa s, and more preferably 200 mPa s to 350,000 mPa s. , More preferably 250 mPa s to 300,000 mPa s, more preferably 300 mPa s to 50,000 mPa s, still more preferably 350 mPa s to 30,000 mPa s, 400 mPa s to 15,000 mPa s Especially preferred. Although the method for adjusting the viscosity of the resin (B) is not particularly limited, for example, a method for adjusting the temperature of the resin (B) can be mentioned. By setting the viscosity of the resin (B) to an optimum value, it is possible to prevent the pressure from becoming too high during transfer, and the shearing step can be carried out efficiently.

Moreover, the temperature of the mixture in the shearing step is not particularly limited. The temperature of the mixture when subjected to the shearing step is, for example, preferably 10°C to 90°C, more preferably 15°C to 80°C, even more preferably 20°C to 70°C, and particularly preferably 20°C to 60°C. The temperature of the mixture obtained by the shearing step is, for example, preferably 10°C to 90°C, more preferably 15°C to 80°C, still more preferably 20°C to 70°C, and particularly preferably 20°C to 60°C. When the temperature of the mixture when subjected to the shearing step and/or the temperature of the mixture obtained by the shearing step is within the above range, there is an advantage that deterioration of the polymer microparticles (A) can be suppressed. In addition, "the temperature of the mixture when subjected to the shearing step" can also be said to be "the temperature of the mixture before the shearing step". Further, "the temperature of the mixture obtained by the shearing step" can be said to be "the temperature of the mixture after the shearing step" or "the temperature of the mixture after the shearing step and before the first separation step". The first separation step will be described later.

The shearing step can be performed in various embodiments and is not particularly limited. For example, (i) a mode in which a shearing device (such as an emulsifier) is installed in a container into which the mixture obtained in the resin mixing step is placed, and (ii) the mixture obtained in the shearing step is circulated. Thus, an aspect in which the step of passing the mixture through a shearing device (emulsifier etc.) is performed multiple times, (iii) an aspect in which the resin mixing step and the shearing step are performed continuously (iv) a flow path for passing the mixture and the resin ( (v) a step of applying shear to the mixture obtained in the resin mixing step by installing a shearing device (such as an emulsifier) after confluence with the flow path through which B) passes; Examples include an embodiment in which the mixture obtained in the shearing step is passed through a shearing device (emulsifier, etc.) multiple times.

(First separation step)
In the shearing step, a coagulate containing fine polymer particles (A) and resin (B) may be obtained. In this case, after the shearing step, a first separation step of separating the mixture obtained in the shearing step into a coagulate and a water component may be performed.

Specific aspects of the first separation step are not particularly limited, and include, for example, methods such as filtration and compression dehydration.

(Coagulant addition step)
The coagulant addition step is a step of adding a coagulant to the mixture obtained by the shearing step. When performing the first separation step, the coagulant addition step may be a step of adding a coagulant to the water component obtained in the first separation step.

The coagulant is not particularly limited. As the coagulant, for example, any substance having properties capable of coagulating and coagulating the polymer fine particles (A) in the latex may be used. Examples of coagulants include (i) inorganic acids (salts) and/or organic acids (salts), (ii) aqueous solutions of inorganic acids (salts) and/or organic acids (salts), and (iii) polymers coagulants and the like. Inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like. Inorganic salts include sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, potassium iodide, sodium iodide, potassium sulfate, sodium sulfate, ammonium sulfate, ammonium chloride, sodium nitrate, potassium nitrate, Calcium chloride, ferrous sulfate, magnesium sulfate, zinc sulfate, copper sulfate, barium chloride, ferrous chloride, ferric chloride, magnesium chloride, ferric sulfate, aluminum sulfate, potassium alum, iron alum, etc. be done. Organic acids include acetic acid, formic acid, and the like. Organic acid salts (organic salts) include sodium acetate, calcium acetate, sodium formate, calcium formate and the like. The polymer coagulant is not particularly limited as long as it is a polymer compound having a hydrophilic group and a hydrophobic group. The polymer coagulant may be, for example, an anionic polymer coagulant, a cationic polymer coagulant, or a nonionic polymer coagulant. As the polymer coagulant, a cationic polymer coagulant is preferable because it can further enhance the effects of one embodiment of the present invention. The cationic polymer coagulant includes a polymer coagulant having a cationic group in its molecule, that is, a polymer coagulant that exhibits cationic properties when dissolved in water. Specific examples of cationic polymer coagulants include polyamines, polydicyandiamides, cationic starch, cationic poly(meth)acrylamide, water-soluble aniline resins, polythiourea, polyethyleneimine, quaternary ammonium salts, polyvinyl Examples include pyridines and chitosan. The coagulants described above may be used alone or in combination of two or more. Among the above-mentioned coagulants, monovalent or divalent inorganic salts or inorganic acids such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride, hydrochloric acid, sulfuric acid, etc. can be preferably used. The method of adding the coagulant is not particularly limited, and may be (a) a method in which the total amount of the coagulant to be added is added at once in a short period of time, or (b) a method in which the total amount of the coagulant to be added is divided into several portions and added for a certain period of time. and (c) a method of continuously adding the total amount of the coagulant to be added little by little.

The amount of the coagulant to be added may be 1 to 50 parts by weight, preferably 2 to 30 parts by weight, more preferably 3 parts by weight, with respect to 100 parts by weight of the mixture. More preferably ~20 parts by weight. Incidentally, the amount of the coagulant to be added can be appropriately changed according to the type of the polymer fine particles (A) and the like.

(Mixing process)
The production method may include a mixing step. A mixing process is a process of mixing the mixture obtained by the coagulant addition process. In the mixing step, the mixture obtained in the coagulant addition step is used to prepare a mixture containing a resin composition, which is a coagulate containing polymer fine particles (A) and resin (B), and an aqueous liquid. It can be rephrased as a process.

The method of mixing the mixture obtained by the coagulant addition step is not particularly limited, and various techniques can be used. Examples of the method include a method of stirring the mixture at 3,000 to 25,000 rpm with a homomixer, a method of stirring the mixture at 500 to 12,000 rpm with a high-shear emulsifier, and a method of stirring the mixture with a high-pressure homogenizer. , a method of stirring the mixture at 100 rpm to 2,000 rpm with a pin mixer. In order to obtain a larger amount of the resin composition, which is a coagulate containing polymer fine particles (A) and resin (B), when using a homomixer, the mixture is stirred at 5,000 rpm to 25,000 rpm. is preferable, stirring at 7,000 rpm to 20,000 rpm is preferable, and stirring at 8,000 rpm to 20,000 rpm is more preferable. When the mixture is stirred with a high-shear emulsifier in order to obtain a larger amount of the resin composition, which is a coagulate containing the polymer fine particles (A) and the resin (B), the mixture is stirred at 1,000 rpm to 12,000 rpm. It is preferable to stir at 2,000 rpm to 20,000 rpm, more preferably 2,500 rpm to 20,000 rpm. When the mixture is stirred with a pin mixer, the mixture is preferably stirred at 150 rpm to 1,500 rpm, preferably 150 rpm to 1,000 rpm, and more preferably 150 rpm to 500 rpm.

When the viscosity of the resin (B) is high, it is preferable to adjust the viscosity of the resin (B) to an optimum viscosity. For example, the optimum viscosity of the resin (B) is preferably 100 mPa s to 750,000 mPa s, more preferably 150 mPa s to 700,000 mPa s, and more preferably 200 mPa s to 350,000 mPa s. , More preferably 250 mPa s to 300,000 mPa s, more preferably 300 mPa s to 50,000 mPa s, still more preferably 350 mPa s to 30,000 mPa s, 400 mPa s to 15,000 mPa s Especially preferred. The method of adjusting the viscosity of the resin (B) is not particularly limited, but examples include a method of adjusting the temperature of the resin (B) (for example, a method of adjusting the temperature of the mixture obtained in the coagulant addition step). be able to. By setting the viscosity of the resin (B) to an optimum value, it is possible to prevent the pressure during transfer from becoming too high, and the mixing process can be carried out efficiently. As a result, a larger amount of the resin composition, which is a coagulate containing the polymer fine particles (A) and the resin (B), can be obtained more efficiently.

Also, the mixing step is preferably carried out in the presence of a gas-liquid interface. According to this configuration, a larger amount of the resin composition, which is a coagulate containing the polymer fine particles (A) and the resin (B), can be obtained more efficiently. In order to carry out the mixing step in the presence of a gas-liquid interface, air bubbles (also referred to as air or bubbles) should be present in the mixture obtained by the coagulant addition step. In other words, the mixing step is preferably carried out while mixing the mixture obtained in the coagulant addition step with gas (for example, air, carbon dioxide and nitrogen).

Moreover, the temperature of the mixture in the mixing step is not particularly limited. The temperature of the mixture when subjected to the mixing step is, for example, preferably 10°C to 90°C, more preferably 15°C to 80°C, still more preferably 20°C to 70°C, and particularly preferably 20°C to 60°C. The temperature of the mixture obtained by the mixing step is, for example, preferably 10°C to 90°C, more preferably 15°C to 80°C, still more preferably 20°C to 70°C, and particularly preferably 20°C to 60°C. When the temperature of the mixture when subjected to the mixing step and / or the temperature of the mixture obtained by the mixing step is within the above range, (a) the advantage that deterioration of the polymer fine particles (A) can be suppressed, and ( b) It has the advantage of being able to obtain a larger amount of the resin composition, which is a coagulate containing the polymer fine particles (A) and the resin (B). In addition, "the temperature of the mixture when subjected to the mixing step" can also be said to be "the temperature of the mixture before the mixing step". Further, "the temperature of the mixture obtained by the mixing step" can be said to be "the temperature of the mixture after the mixing step", or "the temperature of the mixture after the mixing step and before the first separation step".

The mixing step can be performed in various embodiments and is not particularly limited. For example, (i) a mode in which a mixing device (such as an emulsifier) is installed in a container into which the mixture obtained in the coagulant addition step is placed, and (ii) the mixture obtained in the mixing step is circulated. A mode in which the step of passing the mixture through a mixing device (emulsifier, etc.) is performed multiple times, a mode in which the coagulant addition step and the mixing step are performed continuously, (v) installing a mixing device (such as an emulsifier) after the channel for passing the mixture and the channel for passing the coagulant are combined to mix the mixture obtained in the coagulant addition step; In the aspect of (iv), the mixture obtained in the mixing step is passed through a mixing device (such as an emulsifier) multiple times, and (vi) in (iii) to (v), the mixing device (such as an emulsifier) is used. For example, after separating the passed mixture into coagulate and water component, the water component is passed through the mixing apparatus one or more times.

A mixture containing the resin composition and the water-based liquid can be prepared by the resin mixing step, the shearing step, the coagulant addition step and the mixing step described above. The resulting mixture can be subjected to the foam breaking step described below.

(Second separation step)
After the mixing step described above, the mixture obtained in the mixing step is separated into a resin composition, which is a coagulate containing the polymer fine particles (A) and the resin (B), and a water component. steps may be performed. The second separation step can also be rephrased as a step of removing water from the mixture obtained in the mixing step to obtain a resin composition that is a coagulate containing the polymer fine particles (A) and the resin (B). .

The method for separating the coagulate and water component is not particularly limited. For example, methods such as filtration and compression dehydration can be used. In the second separation step after the mixing step, the water component is a mixture containing water as the main component, but also containing an emulsifier, non-coagulated polymer particles (A), resin (B), and the like.

It should be noted that the resin composition obtained by the above-described second separation step may also include lumps of the aqueous liquid. Therefore, since the resin composition obtained in the second separation step can also be said to be a mixture in the foam breaking step, the resin composition (mixture) may be subjected to the foam breaking step.

(Washing process)
After the mixing step described above, a washing step may be performed to wash the precipitate (resin composition) in the mixture obtained in the mixing step. By washing the coagulate (resin composition) in the mixture obtained in the mixing step, a coagulate with a low content of contaminants and the like can be obtained. In the washing step, the coagulate is more preferably washed with water, and more preferably washed with ion-exchanged water or pure water.

In the washing step, washing water may be added to the mixture obtained in the mixing step to wash the coagulate in the mixture without performing the second separation step after the mixing step. Alternatively, in the washing step, after the second separation step performed after the mixing step, washing water may be added to the coagulate obtained in the second separation step to wash the coagulate.

In the washing step, the mixture obtained by the washing step is separated into a coagulate (resin composition) after washing and a water component, and the coagulant and emulsifier derived from the coagulant after washing. It is preferable to include a step of mixing the mixture of the coagulate and the washing water so that the amount of the elements S and P of is 5000 ppm or less with respect to the weight of the coagulate after washing. This configuration has the advantage of obtaining a coagulate with a lower content of contaminants and the like.

It is preferable that the amount of the elements S and P derived from the coagulant and emulsifier in the coagulate after washing is as small as possible. , is more preferably 4,000 ppm or less, even more preferably 3,000 ppm or less, and particularly preferably 2,000 ppm or less.

The coagulate (resin composition) obtained after the washing step can be subjected to the defoaming step.

(2-6. Dehydration step)
The water content of the mixture prepared by the above methods (a1) to (a4) or the mixture obtained in the above washing step may be higher than, for example, 90% by weight. In this case, a dehydration step may be carried out to remove a portion of the aqueous liquid so that the water content of the mixture is 90% by weight or less before the defoaming step of the present separation method.

Specific aspects of the dehydration step are not particularly limited, and examples thereof include methods such as centrifugation and sedimentation. Centrifugation and sedimentation are preferred from the viewpoint of separating the water content to a desired range, and sedimentation is particularly preferred from the viewpoint of more efficient separation.

In the dehydration step, as a method of removing part of the aqueous liquid by centrifugation, there is a method of using a centrifugal separator that utilizes a difference in specific gravity, such as a decanter-type centrifugal separator.

Further, in the dehydration step, as a method for removing a part of the aqueous liquid by sedimentation, the mixture is supplied into a tank, and the resin composition is sedimented using the difference in specific gravity between the resin composition and the aqueous liquid. There is a method of recovery (hereinafter also simply referred to as "precipitation separation method"). A more specific embodiment of the sedimentation separation method may include the following steps (c1) to (c4), but is not limited to such a production method: (c1) the mixture is transferred from the supply unit to the tank (c2) a resin composition recovery step of recovering the resin composition by settling it in the tank due to the difference in specific gravity between the resin composition and the water-based liquid; and (c3) recovering the water-based liquid. water-based liquid recovery process. The sedimentation separation method may further include (c4) a retention step of increasing the retention time of the aqueous liquid in the tank. A mixture with a desired moisture content can be prepared by the sedimentation method. The resulting mixture can be subjected to the defoaming step of the separation method.

(2-7. Resin composition contained in the mixture)
The resin composition contained in the mixture contains the polymer microparticles (A) and the resin (B), and can enclose the water-based liquid as one or more lumps in the resin composition.

From the viewpoint of enjoying the advantages of this separation method, the blending ratio of the fine polymer particles (A) and the resin (B) in the resin composition is preferably set so that the viscosity of the mixture is within the preferred range described above. . Such a compounding ratio varies depending on the types of the polymer fine particles (A) and the resin (B), and is not particularly limited. When the total is 100% by weight, it is preferable that the polymer fine particles (A) are 1 to 70% by weight, the resin (B) is 30 to 99% by weight, and the polymer fine particles (A) are 10 to 60% by weight. %, the resin (B) is more preferably 40 to 90% by weight, the fine polymer particles (A) are more preferably 20 to 50% by weight, and the resin (B) is 80 to 50% by weight. It is more preferable that the combined fine particles (A) are 25 to 45% by weight and the resin (B) is 75 to 55% by weight.

The viscosity of the resin composition is preferably 100 to 1,000,000 mPa s at 25° C., more preferably 1,000 to 200,000 mPa s, and more preferably 1,000 to 50,000 mPa s. is more preferable. A resin composition having a viscosity within the above range has the advantage of exhibiting suitable behavior in the present separation method and being able to be efficiently separated from an aqueous liquid. In other words, this separation method is particularly suitable for separating a resin composition having a viscosity within the above range from an aqueous liquid. In this specification, the viscosities of the resin composition and the water-based liquid may be viscosities obtained by measuring the resin composition and the water-based liquid obtained after separation by the present separation method.

The resin composition may have viscosity. The viscosity of the resin composition is not particularly limited. This separation method has the advantage that the resin composition and the aqueous liquid can be separated even when the resin composition has a certain viscosity. In other words, this separation method can also be suitably used when separating a resin composition having a certain viscosity.

The resin composition preferably has a specific gravity of 950 kg/m ³ to 5,000 kg/m ³ at 25° C., more preferably 1,000 kg/m ³ to 4,000 kg/m ³ , More preferably, it has a specific gravity of 1,050 kg/m ³ to 3,000 kg/m ³ . When the specific gravity of the resin composition is within the above range, there is an advantage that the above-described dehydration step can be easily performed. In this specification, the specific gravity of the resin composition is calculated from the results obtained by preparing a specific gravity standard solution using a standard hydrometer, conducting a floating and sinking test of the resin composition with respect to the obtained specific gravity standard solution. be the obtained value. In this specification, the specific gravity of the resin composition and the aqueous liquid may be the specific gravity obtained by measuring the resin composition and the aqueous liquid obtained after separation by the present separation method.

The resin composition may contain optional components other than the fine polymer particles (A) and the resin (B), if necessary. Other optional components include antiblocking agents, curing agents, colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, heat stabilizers (anti-gelling agents), plasticizers, leveling agents, Antifoaming agents, silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducers, low shrinkage agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, and dispersants.

The resin composition may further contain a known thermosetting resin other than the resin (B), or may further contain a known thermoplastic resin.

(2-8. Aqueous liquid contained in the mixture)
The viscosity of the aqueous liquid contained in the mixture is preferably less than 100 mPa·s, more preferably 20 mPa·s or less, and even more preferably 4 mPa·s or less at 25°C. An aqueous liquid having a viscosity of less than 100 mPa·s has the advantage of exhibiting suitable behavior in the present separation method and being able to be efficiently separated from the resin composition.

The lower limit of the viscosity of the aqueous liquid is not particularly limited, but from the viewpoint that the main component is water, it is preferably 0.3 mPa s or more at 25 ° C., more preferably 0.5 mPa s or more. It is more preferably 0.7 mPa·s or more. In addition, the fact that the main component of the water-based liquid is water means that water accounts for more than 50% by weight in the water-based liquid (100% by weight). 90% by weight or more of the aqueous liquid (100% by weight) may be water.

The viscosity of the aqueous liquid can be adjusted within a desired range by appropriately adjusting the ratio of water contained in the aqueous liquid.

The aqueous liquid preferably has a specific gravity of 900 kg/m ³ to 1,100 kg/m ³ at 25° C., more preferably 950 kg/m ³ to 1,050 kg/m ³ . When the specific gravity of the aqueous liquid is within the above range, there is an advantage that the above-described dehydration step can be easily performed. In this specification, the specific gravity of an aqueous liquid is a value obtained by measuring using a standard hydrometer.

The water-based liquid is a water-based liquid containing impurities that is mixed into the resin composition during the manufacturing process and washing process of the resin composition, the aggregating process of the resin composition, and the washing process of the aggregates (intermediate washing process). you can Impurities contained in the aqueous liquid include substances derived from emulsifiers, coagulants (inorganic salts), metal soaps, and the like used in the production and aggregation of the resin composition, and contaminants (water-soluble compounds). Impurities contained in the aqueous liquid are detected and quantified by measuring the amounts of the elements S, P, Ca, Mg, Fe, Zn, Ba, Al, etc. with a fluorescent X-ray analyzer SPECTROXEPOS (manufactured by SPECTRO). be able to.

(2-9. Defoaming step)
In this separation method, by applying stress to a mixture of a resin composition containing polymer fine particles (A) and a resin (B) and an aqueous liquid, the lumps of the aqueous liquid contained in the mixture are broken. Includes a foam breaking process that allows The foam breaking step can also be said to be a step of removing the water-based liquid from the resin composition containing the water-based liquid mass by breaking the foam of the mass.

The method of applying stress to the mixture is not particularly limited, and various methods can be selected. From the viewpoint of efficiently breaking bubbles by a simple method, the breaking step includes a step of applying stress to the mixture by thinning the mixture, and extruding or sucking the mixture through a nozzle having holes. and the step of applying stress to the mixture.

(Thin film forming process)
The step of applying stress to the mixture by thinning the mixture (hereinafter also simply referred to as the “thin filming step”) includes an ejection portion having an ejection port for ejecting the mixture (for example, a supply pipe for the mixture); and a surface for pressing the mixture expelled from the unit into a thin film. The mixture ejection part used in the thinning process may be hereinafter referred to as a "first ejection part". The first outlet may further comprise a feed pump for pressurizing and pushing out the mixture. Using such a thin film forming system, stress can be applied to the mixture by pressing the mixture discharged from the first discharge section against a surface to form a thin film.

The first discharge part and the surface are not particularly limited as long as they have strength enough to apply stress to the mixture to form a thin film. For example, the cross-sectional area (mm ² ) of the ejection opening of the first ejection section is not particularly limited. Here, the "cross-sectional area of the ejection opening of the first ejection section" is intended to be the area of the cross section of the ejection opening of the first ejection section perpendicular to the ejection direction of the mixture.

Examples of the surface for pressing the mixture discharged from the first discharge part into a thin film include the wall surface of a tank, the belt surface of a belt conveyor, and the like. If the surface is the belt surface of a belt conveyor, it has the advantage that the thinning process can be carried out continuously.

The surface may extend substantially horizontally, or may be inclined to form a predetermined angle with the horizontal direction. When the surface is inclined, the water-based liquid that appears on the resin composition due to the bubble breakage of the mass falls from the surface due to its own weight, while the resin composition having a higher viscosity than the water-based liquid adheres to the surface. This has the advantage of facilitating the separation of the two.

In one embodiment of the invention, it is particularly preferred that the surface is the belt surface of a belt conveyor, the belt surface being inclined and the belt surface flowing from bottom to top. According to this configuration, the water-based liquid that appears on the resin composition due to the bubble breaking of the mass falls from the surface due to its own weight, while the resin composition is conveyed upward while adhering to the belt surface of the belt conveyor. Therefore, there is an advantage that the separation of the two becomes easier.

The distance (clearance) between the ejection port and the surface of the first ejection part is not particularly limited as long as it can apply a stress to the extent that the lumps of the aqueous liquid contained in the mixture can be broken. The shorter the distance between the ejection port of the first ejection part and the surface, the greater the stress applied to the mixture by the thinning step, and the thinner the thickness of the thinned resin composition. The preferred range of the distance varies depending on the viscosity of the mixture, the relationship between the cross-sectional area of the ejection port and the flow rate of the mixture (ie linear velocity), and the like. For example, the distance is preferably 0.1 mm to 100.0 mm, more preferably 0.5 mm to 50.0 mm, because it is possible to efficiently break the bubbles of the aqueous liquid contained in the mixture. More preferably, it is 1.0 mm to 10.0 mm.

Similarly, the linear velocity in the thin film forming step is not particularly limited as long as it can apply stress to the extent that the lumps of the aqueous liquid contained in the mixture can be broken. The higher the linear velocity, the greater the stress imparted to the mixture by the thinning process. A preferred range of the linear velocity in the thinning step varies depending on the viscosity of the mixture, the distance between the ejection port of the first ejection section and the surface, and the like. For example, the linear velocity is preferably from 0.01 m / s to 1.00 m / s, and from 0.05 m / s to It is more preferably 0.50 m/s, and even more preferably 0.10 m/s to 0.30 m/s.

The linear velocity in the thinning process is a value calculated by the following formula.
Linear velocity [m/s]=Flow rate of mixture [m ³ /s]/Cross-sectional area of ejection port of first ejection part [m ² ].

The shorter the distance between the ejection port of the first ejection part and the surface and the higher the linear velocity, the greater the stress applied to the mixture by the thinning process. Since it is possible to efficiently break the bubbles of the water-based liquid contained in the mixture, the linear velocity (m / s) with respect to the distance (mm) between the ejection port and the surface of the first ejection part in the thinning process The ratio of (linear velocity (m / s) / distance (mm)) is preferably 0.0001 to 10.0000, more preferably 0.0010 to 1.0000, 0.0100 to 0 More preferably .1000.

(extrusion or suction process)
The step of extruding or sucking the mixture through a nozzle having a hole (hereinafter also simply referred to as “extrusion or sucking step”) is a discharge part provided with a nozzle having a hole as a discharge port for discharging the mixture (for example, the mixture can be carried out using a separation device with a feed pipe of A discharge section for the mixture used in the extrusion or suction process may hereinafter be referred to as a "second discharge section". The second outlet may further comprise a feed pump for pressurizing and pushing the mixture. Also, the separation device may further comprise a suction pump for sucking the mixture. By using such a separation device and discharging the mixture through the hole provided in the nozzle of the second discharge section, stress can be applied to the mixture.

The number of ejection openings provided in the nozzle of the second ejection section is not particularly limited. Further, the nozzle of the second ejection part may have a plurality of holes with different shapes as ejection ports. The shape of the hole is not particularly limited, and may be circular, elliptical, rectangular, polygonal, slit-shaped, or the like.

The cross-sectional area (mm ² ) of the ejection port of the second ejection part is not particularly limited as long as it can apply stress to the mixture to the extent that the mass of the aqueous liquid contained in the mixture is broken. . The smaller the cross-sectional area, the greater the stress imparted to the mixture by the extrusion or suction process. The preferred range of the cross-sectional area varies depending on the viscosity of the mixture, the relationship between the cross-sectional area of the ejection port of the second ejection part and the flow rate of the mixture (ie, linear velocity), and the like. For example, the cross-sectional area of the ejection port of the ^second ejection part is preferably 1 mm ² to 1,000 mm ² , since the lumps of the aqueous liquid contained in the mixture can be efficiently broken. It is more preferably ˜500 mm ² , and even more preferably 1 mm ² to 100 mm ² . Here, the "cross-sectional area of the ejection port of the second ejection part" intends the area of the cross section of the ejection port of the second ejection part perpendicular to the ejection direction of the mixture.

Similarly, the linear velocity in the extrusion or suction step is not particularly limited as long as the linear velocity is capable of imparting stress to the extent of breaking bubbles in the mass of the aqueous liquid contained in the mixture. The higher the line speed, the greater the stress imparted to the mixture by the foam breaking process. A preferred range of linear velocity in the extrusion or suction process varies depending on the viscosity of the mixture and the like. For example, the linear velocity is preferably from 0.01 m / s to 1.00 m / s, and from 0.05 m / s to It is more preferably 0.50 m/s, and even more preferably 0.10 m/s to 0.30 m/s.

The linear velocity in the extrusion or suction process is a value calculated by the following formula.
Linear velocity [m/s]=flow rate of mixture [m ³ /s]/cross-sectional area of ejection port of second ejection part [m ² ].

In the foam-breaking step, the suitable temperature of the mixture varies depending on the viscosity of the resin composition and the water-based liquid contained in the mixture, and is not particularly limited. In one embodiment, the temperature of the mixture when subjected to the foam breaking step is, for example, preferably 10°C to 90°C, more preferably 15°C to 80°C, and 20°C to 70°C. More preferably, it is particularly preferably from 20°C to 60°C. When the temperature of the mixture is within the above range when subjected to the foam-breaking step (when stress is applied), there is an advantage that the mixture has an appropriate viscosity range and is easily broken.

At the temperature during the foam breaking step, the viscosity of the mixture is preferably 100 mPa·s or more, more preferably 500 mPa·s or more, and even more preferably 1,000 mPa·s or more. Further, at the temperature during the foam breaking process, the viscosity of the mixture is preferably 1,000,000 mPa s or less, more preferably 50,000 mPa s or less, and 30,000 mPa s or less. is more preferred.

The water content of the resin composition obtained after the foam-breaking step is not particularly limited, and varies depending on the water content of the mixture to be subjected to the foam-breaking step. As one embodiment, the water content of the resin composition obtained after the foam breaking step is, for example, 1% to 70% by weight when the weight of the resin composition is 100% by weight. It is more preferably 1 wt % to 50 wt %, even more preferably 1 wt % to 30 wt %, and particularly preferably 1 wt % to 25 wt %.

(2-10. Washing step)
This separation method may further include a washing step of washing the resin composition obtained by the foam breaking step. By washing the resin composition, a resin composition containing less contaminants and the like can be obtained. In the washing step, washing with water is more preferable, and washing with ion-exchanged water or pure water is even more preferable.

The washing step is not particularly limited as long as it is a step of washing the resin composition. For example, a method of mixing the resin composition and water and stirring with a stirrer, a method of kneading the resin composition and water using a kneader, a method of mixing the resin composition and water with a rotation-revolution mixer, Examples include a method of spraying the resin composition and a method of washing the cake with a pressure filter. Various types of kneaders such as batch kneaders, continuous kneaders and extrusion kneaders can be used.

The object to be washed is not particularly limited and is intended to include general impurities contained in the resin composition. Examples thereof include contaminants derived from emulsifiers (for example, phosphorus emulsifiers and sulfonic acid emulsifiers), contaminants derived from flocculants, and the like.

Further, the resin composition and the washed water can be separated by subjecting the mixture of the resin composition obtained by the washing step and the washed water to the dehydration step and/or the foam breaking step again.

[3. Method for producing a resin composition]
A method for producing a resin composition according to an embodiment of the present invention includes [2. Separation method] is included as one step. More specifically, the method for producing a resin composition according to an embodiment of the present invention includes the foam-breaking step described in the section (2-9. Foam-breaking step) as one step. Since the method for producing a resin composition according to one embodiment of the present invention has such a configuration, it has the advantage of being able to efficiently obtain a resin composition containing a small amount of water-based liquid containing impurities. Moreover, the resin composition obtained by the method for producing a resin composition according to one embodiment of the present invention has the advantage that the amount of water-based liquid containing impurities mixed therein is small.

Regarding the method for producing a resin composition according to an embodiment of the present invention, other than the matters described above, [2. Separation method].

A cured product obtained by curing the resin composition obtained by the method for producing a resin composition according to one embodiment of the present invention has high dispersion stability of the polymer fine particles (A) and contains few impurities. The cured product is also one embodiment of the present invention.

The resin composition obtained by the method for producing a resin composition according to one embodiment of the present invention can be used for various uses, and the uses are not particularly limited. The resin composition includes, for example, adhesives, coating materials, reinforcing fiber binders, composite materials, molding materials for 3D printers, sealing agents, electronic substrates, ink binders, wood chip binders, rubber chip binders, foam chip binders, It is preferably used for applications such as binders for castings, bedrock consolidation materials for flooring and ceramics, and urethane foams. Examples of urethane foam include automobile seats, automobile interior parts, sound absorbing materials, damping materials, shock absorbers (shock absorbing materials), heat insulating materials, construction floor material cushions, and the like. Among the applications described above, the resin composition is more preferably used as an adhesive, a coating material, a binder for reinforcing fibers, a composite material, a molding material for 3D printers, a sealant, and an electronic substrate.

EXAMPLES Hereinafter, one embodiment of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. One embodiment of the present invention can be modified and implemented as long as it conforms to the spirit of the above and later descriptions, and all of them are included in the technical scope of the present invention.

[Evaluation method]
First, the method for evaluating the resin composition produced in Production Examples and the method for evaluating the resin composition and water-based liquid recovered in Examples and Comparative Examples will be described.

<Measurement of volume average particle size>
The volume average particle size (Mv) of the elastic body or polymer fine particles (A) dispersed in the aqueous latex was measured using Nanotrac WaveII-EX150 (manufactured by Microtrack Bell Co., Ltd.). A water-based latex diluted with deionized water was used as a measurement sample. For the measurement, water and the refractive index of the elastic body or polymer fine particles (A) obtained in each production example are input, the measurement time is 120 seconds, and the sample concentration is adjusted so that the loading index is within the range of 1 to 20. I adjusted.

<Viscosity>
Resin (B) [liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828)], water-based liquid and mixture used in the following examples and comparative examples were measured for viscosity. The device used was a digital viscometer DV-II+Pro type manufactured by BROOKFIELD. Also, depending on the viscosity range, the viscosity was measured using a spindle CPE-52Z at a measurement temperature of 25° C. while changing the shear rate as necessary. As a result, the viscosity of the liquid epoxy resin (JER828), which is the resin (B), was 12,000 mPa·s at 25°C.

<Water content of resin composition>
The water content of the resin composition was calculated by the following method: (1) the resin composition was dried at 80°C for 3 hours using a hot air dryer, and the weight was measured; (2) the measured weight. was subtracted from the initial weight (the weight of the resin composition before drying), the resulting difference was divided by the initial weight, and the resulting quotient was multiplied by 100.

<Specific gravity of resin composition>
The specific gravity of the resin composition at 25 ° C. is obtained by preparing a specific gravity standard solution using a standard hydrometer, conducting a floating and sinking test of the resin composition with respect to the obtained specific gravity standard solution, and calculating from the obtained results. was the value obtained. A sodium sulfate aqueous solution was used as a specific gravity standard solution.

<Specific gravity of aqueous liquid>
The specific gravity of the aqueous liquid at 25°C was measured using a standard hydrometer.

[Manufacturing example]
(Production Example 1) Production of resin composition containing fine polymer particles (A) and resin (B)1. Polymerization of elastic body Production Example 1-1; Preparation of aqueous latex (R-1) containing elastic body mainly composed of polybutadiene rubber In a pressure-resistant polymerization vessel, deionized water 200 parts by weight, tripotassium phosphate 0.03. 0.002 parts by weight of disodium ethylenediaminetetraacetate (EDTA), 0.001 parts by weight of ferrous sulfate heptahydrate, and 1.55 parts by weight of sodium dodecylbenzenesulfonate (SDBS) as an emulsifier. did. Next, oxygen was sufficiently removed from the inside of the pressure-resistant polymerizer by replacing the gas inside the pressure-resistant polymerizer with nitrogen while stirring the introduced raw materials. After that, 100 parts by weight of butadiene (Bd) was charged into the pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C. After that, 0.03 parts by weight of paramenthane hydroperoxide (PHP) was charged into the pressure-resistant polymerization vessel, and then 0.10 parts by weight of sodium formaldehyde sulfoxylate (SFS) was charged into the pressure-resistant polymerization vessel to initiate polymerization. started. After 15 hours from the start of the polymerization, devolatilization was performed under reduced pressure to remove residual monomers that were not used in the polymerization, thereby completing the polymerization. During the polymerization, each of PHP, EDTA and ferrous sulfate heptahydrate was added in an arbitrary amount and at an arbitrary timing into the pressure-resistant polymerization vessel. By the polymerization, an aqueous latex (R-1) containing an elastic body containing polybutadiene rubber as a main component was obtained. The volume average particle size of the elastic body contained in the obtained aqueous latex (R-1) was 90 nm.

Production Example 1-2; Preparation of water-based latex (R-2) containing elastic body mainly composed of polybutadiene rubber Into a pressure-resistant polymerization vessel, 7 parts by weight of solid content of the water-based latex (R-1) obtained above was added. , 200 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of EDTA, and 0.001 parts by weight of ferrous sulfate heptahydrate were added. Next, oxygen was sufficiently removed from the inside of the pressure-resistant polymerizer by replacing the gas inside the pressure-resistant polymerizer with nitrogen while stirring the introduced raw materials. After that, 93 parts by weight of Bd was put into the pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C. After that, 0.02 parts by weight of PHP was charged into the pressure-resistant polymerization vessel, and then 0.10 parts by weight of SFS was charged into the pressure-resistant polymerization vessel to initiate polymerization. After 30 hours from the start of the polymerization, devolatilization was performed under reduced pressure to remove residual monomers that were not used in the polymerization, thereby completing the polymerization. During the polymerization, each of PHP, EDTA, ferrous sulfate heptahydrate and SDBS was added into the pressure-resistant polymerization vessel at arbitrary amounts and at arbitrary times. By the polymerization, a water-based latex (R-2) containing an elastic body composed mainly of polybutadiene rubber was obtained. The volume-average particle size of the elastic body contained in the obtained aqueous latex (R-2) was 195 nm.

2. Preparation of polymer microparticles (A) (polymerization of graft portion)
Production Example 1-3; Preparation of aqueous latex (L-1) containing fine polymer particles Into a glass reactor, 250 parts by weight of the aqueous latex (R-2) (87 parts by weight of an elastic body mainly composed of polybutadiene rubber) was added. ), and 50 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.20 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. After that, a mixture of 12.5 parts by weight of methyl methacrylate (MMA), 0.5 parts by weight of styrene (St), and 0.035 parts by weight of t-butyl hydroperoxide (BHP) was placed in a glass reactor for 80 minutes. was added continuously over a period of time. After that, 0.013 parts by weight of BHP was added into the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. By the above operation, an aqueous latex (L-1) containing fine polymer particles (A) and an emulsifier was obtained. The polymerization conversion rate of the monomer component was 99% by weight or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-1) was 200 nm. The solid content concentration (concentration of fine polymer particles (A)) in the obtained aqueous latex (L-1) was 30% by weight with respect to 100% by weight of the aqueous latex.

Production Example 1-4; Production of Resin Composition Containing Polymer Fine Particles (A) and Resin (B) 60 kg of water-based latex (L-1) and resin (B) liquid epoxy resin (Mitsubishi Chemical Corporation, JER828 ) was mixed with 27 kg to obtain a mixture (resin mixing step). Then, a shearing stress was applied to the obtained mixture to obtain a latex containing a resin composition, which is an aggregate containing polymer fine particles (A) and resin (B) (shearing step). In the shearing step, a high-shear emulsifier (clearance between the stirring blade and the wall surface of the device: 840 μm) was used as the shearing device, and the rotation speed of the shearing device was 3,600 rev/min, and the residence time of the mixture in the shearing device was 1.1. seconds.

12 kg of a 15% sodium sulfate aqueous solution was added as a coagulant to the mixture obtained in the shearing step to obtain a mixture (coagulant addition step). The resulting mixture was mixed using a pin mixer (1600 times/rev at which rotor pins and stator pins intersect in one rotation) at a rotation speed of 300 rev/min and a residence time of the mixture in the mixer of 12 seconds (mixing process ).

The mixture obtained by mixing was separated into a coagulate (resin composition) and a water component (second separation step). The solid content concentration of the obtained water component was 0.03% by weight. Moreover, the content of the polymer fine particles (A) in 100% by weight of the coagulate (resin composition) was 29.6% by weight. On the other hand, the water content of the coagulate (resin composition) was 26% by weight. Further, the coagulate (resin composition) is composed of 40% by weight of the fine polymer particles (A) and 40% by weight of the resin (B ) contained 60% by weight.

The specific gravity of the resin composition was 1,050 kg/m ³ at 25°C. Moreover, the viscosity of the resin composition was 50,000 mPa·s at 25°C.

(Production Example 2) Production of a mixture of a resin composition and an aqueous liquid The resin composition obtained in Production Example 1 above is put into a container having a pump suction port at the bottom, and a pin mixer is run at a flow rate of 4 kg per minute. was sent to Similarly, deionized water was fed at a flow rate of 15 kg/min, and the two liquids were mixed with a pin mixer. The mixing conditions of the pin mixer were such that the number of interlaced rotor pins and stator pins per rotation was 1,600 times/rev, the number of revolutions was 300 rev/min, and the residence time of the mixture in the mixer was 12 seconds. (washing process). A mixture in which the two liquids were mixed (that is, a mixture containing the resin composition and the aqueous liquid) was obtained from the pin mixer.

The specific gravity of the water-based liquid was almost the same as that of deionized water (E), which was 1,010 kg/m ³ at 25°C. The viscosity of the water-based liquid was approximately the same as that of deionized water (E), and was 1 mPa·s at 25°C.

In 100% by weight of the mixture, the amount of the resin composition was 20% by weight, and the amount of the water-based liquid was 80% by weight. The viscosity of the mixture was 100 mPa·s or more at 25°C. In addition, the difference in specific gravity between the resin composition and the water-based liquid in the mixture was 40 kg/m ³ at 25°C.

[Example 1]
(Dehydration process)
A tank having a supply section, a resin composition recovery section, and an aqueous liquid recovery section was prepared. The resin composition recovery section was equipped with a pump and valves and was located at the lowest position on the bottom of the tank. The water-based liquid recovery part was arranged on the wall surface of the body facing the supply part at the height of the operating water level in the tank.

100 kg of the mixture produced in Production Example 2 was continuously supplied from the gas phase into the vessel at 35° C. and a flow rate of 0.62×10 ⁻³ m ³ /s (mixture supply step). In the mixture supply step, the mixture was supplied from above the operating water level. The linear velocity of the supply speed was 0.15 m/s. The mixture supplied into the tank was separated into a resin composition and an aqueous liquid due to the difference in specific gravity, and the resin composition precipitated at the bottom of the layer. The precipitated resin composition was continuously recovered from the resin composition recovery section by pumping it out of the tank (resin composition recovery step).

On the other hand, the water surface in the tank reached the operating water level, and then the aqueous liquid was continuously recovered from the aqueous liquid recovery part by overflowing to the outside of the tank (aqueous liquid recovery step).

When the water content of the resin composition recovered in the resin composition recovery step was measured, it was 26.3% by weight.

(Foam breaking process)
In the resin composition recovery step, the resin composition recovered from the resin composition recovery section (a resin composition containing lumps of aqueous liquid, in other words, a mixture of the resin composition and the aqueous liquid). was passed through the pipe and extruded at a linear velocity of 0.1 m/s from a nozzle (having one rectangular hole of length x width: 6 mm x 300 mm) located at the tip. As a result, a stress was applied to the resin composition to break the lumps of the water-based liquid contained in the resin composition (extrusion or suction step). The water-based liquid was removed from the mixture of the extruded resin composition and the water-based liquid exposed by breaking the bubbles, and the resin composition was recovered. The moisture content of the recovered resin composition was measured. Table 1 shows the results.

[Example 2]
Example 1 except that in the foam breaking step, a nozzle having one circular (diameter 25 mm) hole was used instead of the nozzle having one rectangular hole, and the line speed was set to 0.3 m / s. A dehydration step and a defoaming step (extrusion or suction step) were carried out by the same method as above, and the resin composition was recovered. The moisture content of the recovered resin composition was measured. Table 1 shows the results.

[Example 3]
In the bubble breaking step, instead of the nozzle having one rectangular hole, a nozzle having 10 slits (opening area: 50 mm ² ) was used, and the line speed was set to 0.3 m/s. By the same method, a dehydration step and a foam breaking step (extrusion or suction step) were performed to recover the resin composition. The moisture content of the recovered resin composition was measured. Table 1 shows the results.

[Example 4]
(Dehydration process)
A dehydration step was performed by the same method as in Example 1, and the resin composition was recovered from the resin composition recovery section at the bottom of the tank.

(Brothing process)
The resin composition recovered from the resin composition recovery unit (a resin composition containing a mass of aqueous liquid, in other words, a mixture of the resin composition and the aqueous liquid) is passed through the pipe, A thin film was pressed onto the inclined surface of the sedimentation tank wall surface from a nozzle (having the same cross-sectional area as the resin composition recovery section) located at the tip. As a result, stress was applied to the resin composition, and bubbles of the water-based liquid included in the resin composition were broken (thin film formation step). The distance between the outlet of the nozzle and the inclined surface was 10 mm, and the linear velocity was 0.1 m/s. The water-based liquid exposed by the bubble breakage dropped from the inclined surface by its own weight, while the resin composition having viscosity and adhesiveness adhered to the surface. The resin composition adhering to the surface was recovered, and its water content was measured. Table 1 shows the results.

In Examples 1 to 4, it can be said that the method for producing a resin composition according to one embodiment of the present invention, which includes the foam breaking step according to one embodiment of the present invention as one step, was performed.

[Comparative Example 1]
By the same method as in Example 1, the mixture supply step, the resin composition recovery step, and the water-based liquid recovery step were performed. The resin composition recovered from the resin composition recovery unit (a resin composition containing a mass of aqueous liquid) is passed through the pipe and is fed to the nozzle located at the tip (the same cross-sectional area as the mixture supply unit 1.795 × It was extruded at a line speed of 0.1 m/s from a nozzle of 10 ⁻³ m ² . That is, in Comparative Example 1, since no stress was applied to the resin composition, the bubbles of the water-based liquid mass did not break, and the collected resin composition contained the water-based liquid mass. When the water content of the recovered resin composition was measured, it was 26.3% by weight. was the same. Table 1 shows the results.

In Examples 1 to 4, a resin composition with a low water content could be efficiently obtained by performing the foam breaking step. On the other hand, the resin composition obtained in Comparative Example 1 had a high water content and still included lumps of the aqueous liquid.

According to one embodiment of the present invention, it is possible to provide a method capable of efficiently separating a resin composition and an aqueous liquid from a mixture of a resin composition containing polymer fine particles and a resin and an aqueous liquid. Therefore, the separation method according to one embodiment of the present invention includes adhesives, coating materials, binders for reinforcing fibers, composite materials, molding materials for 3D printers, sealants, electronic substrates, ink binders, wood chip binders, and rubber chip binders. It can be suitably used as one step of producing a resin composition that is preferably used for applications such as binders, foam chip binders, binders for castings, bedrock consolidation materials for floor materials and ceramics, and urethane foams.

Claims (9)

A method for separating a resin composition and an aqueous liquid from a mixture of a resin composition containing polymer fine particles (A) and a resin (B) and an aqueous liquid,
The mixture includes the resin composition encapsulating the water-based liquid mass,
A separation method, comprising a foam-breaking step of breaking the lumps of the aqueous liquid by applying stress to the mixture. The foam-breaking step includes applying stress to the mixture by thinning the mixture, and applying stress to the mixture by extruding or sucking the mixture through a nozzle having holes. 2. The separation method according to claim 1, comprising at least one step selected from the group consisting of: The separation method according to claim 1 or 2, wherein the viscosity of the mixture is 100 mPa·s or more at 25°C, and the viscosity of the aqueous liquid is less than 100 mPa·s at 25°C. 4. The polymer fine particle (A) according to any one of claims 1 to 3, which is a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body. separation method. The graft portion contains, as structural units, structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers. 5. The separation method according to claim 4, wherein the polymer comprises: The separation method according to claim 4 or 5, wherein the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber. 7. Any one of claims 1 to 6, wherein the resin (B) is liquid, semisolid or solid with a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C. Separation method described in section. The separation method according to any one of claims 1 to 7, wherein the resin (B) is an epoxy resin. A method for producing a resin composition containing fine polymer particles (A) and a resin (B), comprising the separation method according to any one of claims 1 to 8 as one step.