JP2001214069A - Resin composition - Google Patents

Abstract

(57) [Problem] To provide a highly rigid, whitened or opaque molded article without impairing the inherent lightness, excellent mechanical properties and optical properties (surface gloss and color tone) inherent in resin materials. To provide a resin composition from which is obtained. The present invention provides a resin composition comprising a resin and cationic hollow crosslinked polymer particles having a zeta potential measured in an aqueous medium having a pH of 2 to 9 in a range of +5 to +100 mV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition comprising a resin and cationic hollow crosslinked polymer particles having specific physical properties.

[0002]

2. Description of the Related Art Inorganic pigments such as calcium carbonate and titanium oxide are added to resin materials such as thermoplastic resins and thermosetting resins in order to impart properties such as hardness, rigidity, whitening and opacity. ing. When these inorganic pigments are used, the inorganic material has a high specific gravity, and has a disadvantage of impairing the inherent lightness of the resin material. As one of the methods for remedying this drawback, a method using hollow polymer particles has been attempted. However, conventionally used hollow polymer particles are anionic,
In addition, since many of the resin materials are anionic, the affinity between the two is not sufficient, and the improvement of the above performance is insufficient. Had.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin material having high rigidity, whitening, or the like without impairing the inherent light weight, excellent mechanical properties and optical properties (surface gloss and color tone) inherent in the resin material. An object of the present invention is to provide a resin composition from which an opaque molded article can be obtained.

According to the present invention, the above object of the present invention is achieved by providing a resin composition having the following constitution. 1. A resin composition comprising a resin and cationic hollow crosslinked polymer particles having a zeta potential measured in an aqueous medium having a pH of 2 to 9 in a range of +5 to +100 mV. 2. The cationic hollow crosslinked polymer particles are composed of 5 to 90% by weight of a structural unit derived from a crosslinkable monomer and 9 structural units derived from another monomer copolymerizable with the crosslinkable monomer.
5 to 10% by weight (the total amount of both is 100% by weight
The resin composition according to the above 1, wherein the resin composition comprises: 3. The cationic hollow crosslinked polymer particles are (1) 1 to 100% by weight of a crosslinkable monomer, (b) 0 to 15% by weight of a cationic monomer, and (c) copolymerizable using a radical polymerization initiator. 0-99% by weight of a non-crosslinkable and non-ionic monomer (total weight of the monomers is 100% by weight) is polymerized in the presence of polymer particles swellable on at least one of these monomers And (2) the polymer particles are (b) 0 to 30% by weight of a cationic monomer and (d) copolymerizable with the cationic monomer using a radical polymerization initiator. It is a polymer particle obtained by polymerizing 70 to 100% by weight of ionic monomer (the total weight of the monomer is 100% by weight), and (3) the above (1) and (2) The one or resin composition according to 2, characterized in that one or both of the radical polymerization initiator that is a radical initiator having a cationic group.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the resin composition of the present invention will be described in more detail. First, components constituting the resin coating composition will be described.

[Cationic Hollow Crosslinked Polymer Particles] Cationic hollow crosslinked polymer particles (hereinafter simply referred to as “hollow crosslinked particles”)
Has a zeta potential of +5 to +100 mV, preferably +10 to +6, measured in an aqueous medium having a pH of 2 to 9.
It is in the range of 0 mV. In a preferred embodiment, the hollow crosslinked particles have a volume hollow ratio of preferably 1 to 80%, more preferably 3 to 40%, and an average particle diameter of preferably 0.03 to 10 µm, more preferably 0.1 to 10%. The particles are in the range of 1-5 μm.

The zeta potential is an index indicating the ionicity of the particles. The fact that the zeta potential of the hollow crosslinked particles of the present invention is in the above range indicates that the particles have cationicity in a wide range of acidic to alkaline environments. ing. That is, even under a wide range of atmosphere from acidic to alkaline, it exhibits a strong bonding force with the anionic matrix resin. The measurement of the zeta potential of the hollow crosslinked particles is performed by the following method. (Measurement method of zeta potential) The aqueous dispersion of particles was diluted with a 0.1N aqueous potassium chloride solution so that the particle solid content concentration was 0.1% by weight, and this was diluted with hydrochloric acid or potassium hydroxide to pH 2,6. , 9 and the zeta potential at each pH is measured with a laser Doppler zeta potential meter.

The volume hollow ratio is a volume ratio of pores to particles, and as described above, is preferably in the range of 1 to 80%. When the volume hollow ratio is less than 1%, it does not substantially function as hollow crosslinked particles. Also. When the volume hollow ratio exceeds 80%, the strength decreases, which is not preferable. In the present invention, the measurement of the volume hollow ratio is performed by the following method. (Measurement method of volume hollow ratio) An aqueous dispersion of particles was diluted with distilled water so that the particle solid content concentration was 0.1% by weight, and this was dropped on a copper mesh provided with a collodion film and dried.
The particles are photographed with a transmission electron microscope, the inner diameter and the outer diameter of 100 hollow crosslinked particles are measured from the obtained photograph, and the cube of the ratio of the obtained average inner diameter to the average outer diameter is defined as the volume hollow ratio. .

As described above, the average particle size of the hollow crosslinked particles is preferably in the range of 0.03 to 10 μm, and is in the form of fine particles. When the particle diameter is in this range, favorable results can be obtained in terms of dispersibility in the matrix resin, strength, and stability of the dispersion. Hollow crosslinked particles having an average particle diameter of less than 0.03 μm are difficult to produce, while an average particle diameter of more than 10 μm is not preferred because mechanical strength is reduced. In the present invention, the average particle size is measured by the following method (measurement method of average particle size) An aqueous dispersion of particles is appropriately diluted with distilled water, and averaged using a dynamic light scattering particle size analyzer. Measure the particle size.

Such cationic hollow crosslinked polymer particles exhibit a strong bonding force with an anionic matrix resin even in a wide range of atmosphere from acidic to alkaline,
Moreover, since it has sufficient strength and dispersibility, it is excellent as a resin filler or a white pigment. The hollow crosslinked particles preferably further have the following properties. First,
It preferably has solvent resistance to organic solvents such as toluene and alcohol. By having solvent resistance, there is an advantage that when dispersed in a solvent and blended with a resin, the shape of the particles is maintained. Specifically, it is preferable that the amount dissolved in toluene at 25 ° C. is 10% or less. Further, it is preferable to have heat resistance. By having heat resistance, there is an advantage that the shape of the particles is maintained even in a dispersion step (for example, a kneading step) at a high temperature when used as a filler. Specifically, a thermobalance (T
Preferably, the 10% reduction temperature is 240 ° C. or higher as measured by GA). Such solvent resistance and heat resistance,
It can be expressed by appropriately selecting the monomer species.

Examples of the polymer constituting the cationic hollow crosslinked polymer particles include acrylic resins, polystyrene resins, polyolefin resins, polyester resins, polycarbonate resins, polyurethane resins, phenol resins, epoxy resins, and ionomers. Thermoplastic resins or thermosetting resins such as resin, vinyl chloride resin, fluororesin, and butadiene resin are exemplified. It is essential that at least a part of the polymer constituting the hollow crosslinked particles has a cationic group. In the present invention, the cationic group includes a group capable of forming a cation by bonding to a proton such as an amino group and a group in which the group reacts with an acid to form a salt and form a cation portion of the salt. . Specific examples of the cationic group include a primary amino group, a secondary amino group, and a tertiary amino group; a quaternary amino group, a secondary imino group, a tertiary imino group, and a quaternary imino group; an amidino group and an imidino group of each grade. And a hydrazino group; and a cyclic group containing a nitrogen atom such as a pyridyl group.

The concentration of the cationic group in the hollow crosslinked particles is preferably from 0.05 to 300 mmol / 100 g particles, more preferably from 1 to 100 mmol / 100 g particles.

The hollow crosslinked particles preferably comprise a structural unit derived from a crosslinkable monomer and a structural unit derived from another monomer copolymerizable with the crosslinkable monomer. The proportion of the structural unit derived from the crosslinkable monomer is preferably 5 to 90% by weight, more preferably 1 to 90% by weight.
0 to 60% by weight, particularly preferably 15 to 50% by weight, and the proportion of structural units derived from other monomers is preferably 95 to 10% by weight, more preferably 90 to 4% by weight.
It is 0% by weight, particularly preferably 85 to 50% by weight (where the total amount of both structural units is 100% by weight). The existence of the structure derived from the crosslinkable monomer in the hollow crosslinked particles in the above range as described above means that the hollow crosslinked particles have a large number of crosslinked structures, and the strength and heat resistance of the hollow crosslinked particles are improved. , With favorable results. Here, the ratio of the structural unit derived from the crosslinkable monomer to the structural unit derived from another monomer is a value as an average of all the polymers constituting the hollow crosslinked particles.
For example, in the following production methods (I) to (IV), which are preferred methods for obtaining hollow crosslinked particles, polymerization is carried out in the presence of a polymer of swellable polymer particles and the swellable polymer particles. The above ratio is calculated as an average value with the polymer.

The method for producing the cationic hollow crosslinked polymer particles of the present invention is not particularly limited, but the following production methods (I) to (IV) are preferred.

Hereinafter, these production methods (I) to (IV) will be described. First, the monomers (a) to (d) used in the production methods (I) to (IV), the radical polymerization initiator having a cationic group, and the like will be described in detail. <Monomer> (a) Crosslinkable monomer divinylbenzene, divinylbiphenyl, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth)
Acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 2,2′-bis [4- (meth) acryloyloxypropoxyoxyphenyl] propane, 2,2′-bis [4
-(Meth) acryloyloxydiethoxyphenyl] propane, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and other divinyl monomers, trivinyl monomers and tetravinyl monomers Is mentioned. Among them, divinylbenzene,
Preference is given to ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. These can be used alone or in combination of two or more.

(B) Cationic monomer 2-dimethylaminoethyl (meth) acrylate, 2-
Aminoalkyl group-containing (meth) acrylates such as diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, and 3-dimethylaminopropyl (meth) acrylate; and methylene chloride, dimethyl sulfate, and diethyl sulfate thereof. 4 by etc.
Grade salt; 2- (dimethylaminoethoxy) ethyl (meth)
Aminoalkoxyalkyl group-containing (meth) acrylates such as acrylate, 2- (diethylaminoethoxy) ethyl (meth) acrylate, and 3- (dimethylaminoethoxy) propyl (meth) acrylate; and methylene chloride, dimethyl sulfate, and sulfuric acid thereof. Quaternary salts with diethyl and the like; N- (2-dimethylaminoethyl) (meth) acrylamide, N- (2-diethylaminoethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, N- N- such as (3-dimethylaminopropyl) (meth) acrylamide
Aminoalkyl group-containing (meth) acrylamides and quaternary salts thereof with methylene chloride, dimethyl sulfate, diethyl sulfate and the like can be mentioned. Among them, 2-dimethylaminoethyl (meth) acrylate, N- (2-dimethylaminoethyl) (meth) acrylamide, and quaternary salts thereof with methylene chloride are preferable. These can be used alone or in combination of two or more.

(C) Non-crosslinkable and nonionic monomer capable of being copolymerized Here, (c) the noncrosslinkable and nonionic monomer which can be copolymerized includes the above (a) a crosslinkable monomer or (b) a cation. Non-crosslinkable and nonionic monomers that can be copolymerized with any of the hydrophilic monomers. Examples of such a monomer include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, and halogenated styrene; unsaturated nitriles such as acrylonitrile; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and butyl. Acrylate, butyl methacrylate, cyclohexyl methacrylate, 2
-Acrylates and methacrylates such as ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; diolefins such as butadiene and isoprene; Carboxylic acid vinyl esters such as vinyl acetate; and vinylidene halides such as vinyl chloride and vinylidene chloride. Among them, styrene, α-methylstyrene, acrylonitrile, methyl methacrylate, butyl methacrylate, and 2-hydroxyethyl acrylate are preferred. These monomers are
One type may be used alone, or two or more types may be used in combination.

(D) Nonionic monomer copolymerizable with the above (b) cationic monomer This monomer is the same as the above (a) crosslinked except that it satisfies the condition that it can be copolymerized with the (b) cationic monomer. The same as the nonionic monomer and (c) the copolymerizable non-crosslinkable and nonionic monomer. Specific examples thereof include the monomers exemplified as (a) a crosslinkable monomer and (c) a copolymerizable non-crosslinkable and nonionic monomer, including preferable monomers. However, the crosslinkable monomer is used as needed within a range that does not impair the achievement of the object of the present invention. These monomers can be used alone or in combination of two or more.

<Radical polymerization initiator having a cationic group> In the radical polymerization initiator, a polymer obtained by radical polymerization using the radical polymerization initiator has a cationic group derived from the radical polymerization initiator at its terminal. Things. Preferred examples of the radical polymerization initiator having a cationic group include an azobis-type initiator having an amidino group, an imidino group or a pyridium group. Also, 1
Those having a 0-hour half-life temperature in the range of 40 to 95 ° C. are preferred because the polymerization can be carried out under mild conditions. Preferred specific examples of the radical polymerization initiator having a cationic group include the following.

2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-545) 2,2'-azobis [N- (4-chlorophenyl) -2
-Methylpropionamidine] dihydrochloride (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-546)-2,2'-azobis [N- (4-hydroxyphenyl)
-2-Methylpropionamidine] dihydrochloride (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-548). 2,2'-azobis [2-methyl-N- (phenylmethyl) -propionamidine] dihydrochloride. (Sold as VA-552 from Wako Pure Chemical Industries, Ltd.) 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride (from Wako Pure Chemical Industries, Ltd.)・ Sold as VA-553 (trade name) ・ 2,2′-azobis (2-methylpropionamidine)
Dihydrochloride (trade name V from Wako Pure Chemical Industries, Ltd.)
-2,2'-azobis [N- (2-hydroxyethyl)-
2-Methylpropionamidine] dihydrochloride (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-558). 2,2'-azobis [N- (2-carboxyethyl)-
2-Methylpropionamidine] hydrate (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-057)

2,2'-azobis [2-methyl- (5-
Methyl-2-imidazolin-2-yl) propane] dihydrochloride (trade name VA- from Wako Pure Chemical Industries, Ltd.)
2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-044). Azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-054) 2,2'-Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-058) -Azobis [2- (5-hydroxy-3,4,4
5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (sold by Wako Pure Chemical Industries, Ltd. under the trade name VA-059) 2,2′-azobis {2- [1- (2-hydroxyethyl) ) -2-Imidazolin-2-yl] propane} dihydrochloride (trade name VA-0 from Wako Pure Chemical Industries, Ltd.)
2,2'-azobis [2- (2-imidazolin-2-yl) propane] (trade name VA- from Wako Pure Chemical Industries, Ltd.)
061) 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] Hydrate (VA-057),
The use of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044) is preferred.

Next, production methods (I) to (IV) for producing cationic hollow crosslinked polymer particles will be described. <Production method (I)> In this method (I), (a) 1 to 99.99% by weight, preferably 5 to 8% by weight of a crosslinkable monomer is used.
0% by weight, more preferably 15 to 70% by weight, (b)
0.01 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight of a cationic monomer, and (c) a copolymerizable non-crosslinkable and nonionic monomer 0 to 0% 99.99% by weight, preferably 10-9
4.99% by weight, more preferably 25 to 84.5% by weight (the total weight of the monomers is 100% by weight) of polymer particles (hereinafter referred to as swellable) with respect to at least one of the monomers used for polymerization. (Hereinafter simply referred to as “swellable polymer particles”) to produce hollow crosslinked particles, preferably by polymerization in an aqueous medium.

In the above method, the mechanism by which the hollow crosslinked particles are formed is not necessarily clear, but, for example, by coexisting a swellable polymer particle in addition to a polymerizable monomer containing a crosslinkable monomer in an aqueous medium,
During polymerization, the volume change occurs when the monomer that has infiltrated into the swellable polymer particles is polymerized and converted into a polymer, and as a result, pores are formed inside the crosslinked polymer, resulting in a hollow body formed by the crosslinked polymer. Is thought to be formed. On the other hand, when no swellable polymer particles are present, no pores are formed. This presumption is considered to apply not only to the manufacturing method (I) but also to other manufacturing methods (II) to (IV).

In the present method, if the amount of (a) the crosslinkable monomer used is too small, less than 1% by weight, the strength of the particles during polymerization becomes insufficient and the whole particles shrink, and the inside of the particles is reduced. Insufficiency of strain due to polymerization shrinkage prevents inner pores from being formed,
Alternatively, even if polymer particles having inner pores are formed, problems such as a decrease in strength occur. If the amount of (a) the crosslinkable monomer used exceeds 99.99% by weight and is excessive, the amount of (b) the cationic monomer used is reduced,
The cationic properties of the hollow crosslinked particles obtained are low. In addition,
(A) The amount of the crosslinkable monomer to be used is a pure product conversion excluding the inert solvent and the monofunctional non-crosslinkable monomer component contained in the commercially available crosslinkable monomer material. (B) If the amount of the cationic monomer used is too small as less than 0.01% by weight, the resulting hollow crosslinked particles will have reduced cationicity, and will not satisfy the above-mentioned conditions regarding the zeta potential. On the other hand, if the amount of the cationic monomer used exceeds 15% by weight and is excessive, it is not preferable because agglomerates are formed during polymerization. (C) The copolymerizable non-crosslinkable and nonionic monomer is a monomer optionally used for changing hydrophilicity or improving heat resistance as desired. If the amount used exceeds 98.9% by weight,
The amount of (a) the crosslinkable monomer or (b) the cationic monomer used is reduced, and the strength and cationicity of the obtained polymer particles are reduced.

In the present invention, "the monomer can swell"
The term means the case where the polymer particles can absorb the monomer, and includes the case where the monomer can dissolve the polymer particle.

As the polymer constituting the swellable polymer particles, at least one selected from styrene homopolymers and styrene copolymers is preferably used. Examples of the styrene copolymer include a copolymer of styrene and at least one selected from acrylates, methacrylates, and acrylonitrile. Among these, a styrene homopolymer or a styrene copolymer containing 50% by weight or more of a styrene component is particularly preferable.

The amount of the swellable polymer particles used is 100% by weight of the total amount of (a) a crosslinkable monomer, (b) a cationic monomer, and (c) a copolymerizable non-crosslinkable and nonionic monomer. 1 to 100 parts by weight per part,
Preferably it is 2 to 50 parts by weight, more preferably 5 to 20 parts by weight. If the amount of the swellable polymer particles is less than 1 part by weight, the volume hollow ratio is reduced, while if the amount of the swellable polymer particles is more than 100 parts by weight, the formation of pores tends to be suppressed. Is generated.

As a method for carrying out the polymerization by allowing the swellable polymer particles to be present in the aqueous dispersion, the above-mentioned (a), (b) and (c) may be added while the swellable polymer particles are dispersed in the aqueous medium. The method of polymerizing after swelling any of the polymerizable monomers of the above) can be preferably employed. In this case, it is highly preferred that the swellable polymer particles function as seed polymer particles and that any of the polymerizable monomers swell well. For that purpose, the polymer constituting the swellable polymer particles preferably has a small molecular weight,
For example, the number average molecular weight is 20,000 or less, preferably 10,000 or less, and more preferably 700 to 7000.

Here, the number average molecular weight is a value in terms of polystyrene measured by dissolving the swellable polymer particles in a good solvent and using the resulting solution for gel permeation chromatography (GPC). When the number average molecular weight of the swellable polymer particles is greater than 20,000, the amount of the monomer that does not swell in the swellable polymer particles increases, and this polymerizes separately from the swellable polymer particles in the aqueous dispersion, thereby resulting in polymer particles having pores. Not only will a large amount of fine particles not be formed be generated, but also the problem that the polymerization system will become unstable will occur.

The average particle diameter of the swellable polymer particles used as the seed polymer particles is 30 to 8 times the average particle diameter (outer diameter) of the cationic hollow crosslinked polymer particles of the present invention.
It is preferably 0%. The particle size of the polymer particles having voids obtained by polymerization using the swellable polymer particles approximately matches the particle size when the swellable polymer particles swell the polymerizable monomer and enlarge. Therefore, by adjusting the particle size of the swellable polymer particles, the amount of the swellable polymer particles used relative to the polymerizable monomer, and the like, the particle size of the hollow crosslinked particles to be produced can be controlled. Specifically, in the production of polymer particles having pores, in order to obtain hollow crosslinked particles having a particle size of 0.06 to 0.6 μm having excellent whiteness and hiding power, 0.1% of swellable polymer particles is required. 03-0.4
A particle having a particle diameter of 0 μm may be used.

The method for preparing such swellable polymer particles is not particularly limited, and for example, a polymerization method such as emulsion polymerization or suspension polymerization using a relatively large amount of a chain transfer agent can be used.

The polymerization of the monomers (a) to (c) in the presence of the swellable polymer particles is preferably carried out in an aqueous medium by an emulsion polymerization method or a suspension polymerization method.

In the above polymerization, a surfactant used in ordinary polymerization, or an organic or inorganic suspension protective agent can be used. Generally, when producing hollow crosslinked particle polymer particles having an average particle size of less than 1 μm,
When mainly using a surfactant to produce hollow crosslinked particle polymer particles having a large average particle diameter of 1 μm or more,
Suspension protectants may be used primarily.

Examples of the surfactant include cationic surfactants such as alkylamines (salts), polyoxyethylene alkylamines (salts), quaternary alkylammonium salts, and alkylpyridinium salts; dodecyldimethylbetaine, alkylimidazo. Amphoteric surfactants such as rhinium betaine; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, ethylene oxide addition derivative of alkylphenol formalin condensate, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkanolamide , Polyoxyethylene fatty acid amide, reactive emulsifier having polyoxyethylene as a hydrophilic group (“ADEKAREASORP NE-20” manufactured by Asahi Denka Kogyo, “Aqualon RN-2” manufactured by Daiichi Kogyo Seiyaku) Nonionic surfactants such as "); and combinations of these systems is preferably used. Anionic surfactants are not suitable for use in the present invention because they tend to form aggregates during polymerization.

Examples of the organic suspension protective agent include hydrophilic synthetic high molecular substances such as polyvinyl alcohol, polyvinylpyrrolidone and polyethylene glycol, natural hydrophilic high molecular substances such as gelatin and water-soluble starch, and carboxymethyl cellulose. Examples include hydrophilic semi-synthetic polymer substances. Further, as the inorganic suspension protective agent, for example, magnesium, barium, phosphates such as calcium, calcium carbonate, magnesium carbonate, zinc white,
Examples include aluminum oxide and aluminum hydroxide.

As the polymerization initiator, either an oil-soluble polymerization initiator or a water-soluble polymerization initiator can be used. When performing polymerization for producing hollow crosslinked particles having a particle diameter of 1 μm or less, it is preferable to use a water-soluble polymerization initiator, whereby monomer droplets having a large particle size that are not swollen by the hollow crosslinked particles are preferably used. Polymerization can be prevented. In the case of performing polymerization for producing hollow crosslinked particles having a particle size exceeding 1 μm, an oil-soluble polymerization initiator is used in order to prevent generation of polymer particles having no unnecessary pores. Is preferred.

Examples of the water-soluble polymerization initiator include persulfates and redox initiators such as hydrogen peroxide-ferrous chloride and cumene hydroperoxide-sodium ascorbate. Examples of the oil-soluble polymerization initiator include benzoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile and the like. Further, the above-mentioned radical polymerization initiator having a cationic group can also be used.

Depending on the combination of the monomers (a), (b) and (c), the polymerization rate may be high. In this case, the polymerization is carried out using a large polymerization vessel and all of the polymerization components are contained in the polymerization vessel. When a so-called batch polymerization method is used in which the polymerization is carried out, it is difficult to control the polymerization temperature, and there is a danger that the polymerization reaction will run away. Therefore, in order to avoid such danger, a so-called increment polymerization method, in which the monomer component is supplied to the polymerization vessel continuously or in a divided state during the polymerization in the state of an emulsion or in the form of an emulsion, may be employed. it can.

After polymerization, the hollow crosslinked particles are separated from the aqueous dispersion and dried to obtain the cationic hollow crosslinked polymer particles of the present invention having pores therein.

According to the production method (I) of the present invention, for example, a hollow body having an average outer diameter (average particle diameter) of 0.03 to 10 μm and an inner diameter of 0.2 to 0.95 times the outer diameter is used. Thus, cationic hollow crosslinked polymer particles having a single void are obtained. This is the same for the production methods (II) to (IV).

Such a production method (I) is preferably used particularly for producing hollow crosslinked particles having a large amount of cationic groups.

<Production method (II)> In production method (II),
Polymerization is carried out using a radical polymerization initiator having a cationic group to give the resulting hollow crosslinked particles cationicity. And (a) 1 to 100% by weight of the crosslinkable monomer, preferably 5 to 80% by weight, more preferably 15 to 70% by weight, and (b) 0 to 15% by weight of the cationic monomer, preferably 0 to 10% by weight And more preferably 0.1 to 10% by weight, and (c) 0 to 99% by weight, preferably 10 to 95% by weight, more preferably 20 to 84.9% by weight of a copolymerizable non-crosslinkable and nonionic monomer. % By weight (the total weight of the monomers is 100% by weight) in the presence of polymer particles swellable with respect to at least one of the monomers used in the polymerization. Almost the same as the production method (I) except that a radical polymerization initiator having a cationic group is used, and the amounts of the monomers (a), (b) and (c) used are slightly different. , Including a process for the preparation of swellable polymer particles, the polymerization process, operating, the conditions are applied that described in the production method (I).

In the production method (II), the polymerizable monomer may be only (a) a crosslinkable monomer, or (b) a cationic monomer and / or (c) a copolymerizable non-crosslinkable and nonionic monomer in combination. You may. (A) when the amount of the crosslinkable monomer used is less than 1% by weight, and (b) when the amount of the cationic monomer used is more than 15% by weight, and (c) non-crosslinkable copolymerizable. Undesirable phenomena that occur when the amount of the ionic and nonionic monomer used exceeds 99% by weight and the like are the same as those described in the production method (I).

The radical polymerization initiator having a cationic group is preferably used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the monomers used in the polymerization.
More preferably, it is 0.5 to 5 parts by weight. The amount used is 0.
If the amount is less than 1 part by weight, the cationic properties of the obtained hollow crosslinked particles decrease, and if it exceeds 10 parts by weight, polymerization becomes unstable, which is not preferable.

The production method (II) is characterized in that hollow crosslinked particles having a small amount of aggregates can be obtained.

<Production method (III)>
This is a method for obtaining the cationic hollow crosslinked polymer particles of the present invention by making the swellable polymer particles in the production method (I) cationic. The swellable polymer particles are
(B) 0.01 to 30% by weight, preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight of cationic monomer
%, And (d) 70 to 99.99% by weight, preferably 85 to 99.9% by weight, more preferably 90 to 9% by weight of a nonionic monomer copolymerizable with the cationic monomer.
It is obtained by polymerizing 99% by weight (the total weight of the monomers is 100% by weight). The swellable polymer particles include the following monomers (a), (b),
It can swell to any of (c). And, in the presence of the cationic swellable polymer particles,
(A) 1 to 100% by weight, preferably 5% by weight of a crosslinkable monomer
To 80% by weight, more preferably 15 to 70% by weight,
(B) 0 to 15% by weight, preferably 0 to 10% by weight, more preferably 0.1 to 10% by weight of a cationic monomer, and (c) 0 to 95% of a copolymerizable non-crosslinkable and nonionic monomer. % By weight, preferably from 10 to 90% by weight, more preferably from 20 to 84.9% by weight (the total amount of monomers is 100% by weight). Therefore, the production method (III) uses the above-mentioned swellable polymer particles and the production method (I
It is almost the same as the production method (I) except that the amount of the polymerization monomers (a), (b) and (c) used is slightly different from that in the case of I). What has been said in method (I) applies.

In preparing the cationic swellable polymer particles by polymerization, the method of preparing swellable polymer particles described in the production method (I) can be applied. The amount of the monomer (b) used for preparing the cationic swellable polymer particles is less than 0.01% by weight (the amount of the monomer (d) is 99.99).
In the case where the amount of the monomer (b) exceeds (by weight), the cationic hollow crosslinked polymer particles of the present invention obtained have a reduced cationicity, and the amount of the monomer (b) exceeds 30% by weight (excess of the monomer (d)). If the amount is too small (less than 70% by weight), the polymerization becomes unstable, which is not preferable.

The polymerization of the production method (III) is carried out by the production method (I)
As in the case of I), the polymerization monomer may be only (a) a crosslinking monomer, and (b) a cationic monomer and / or
Alternatively, (c) a copolymerizable non-crosslinkable and nonionic monomer may be used in combination. (A) when the amount of the crosslinkable monomer used is less than 1% by weight, and (b) when the amount of the cationic monomer used is more than 15% by weight,
(C) Undesirable phenomena that occur when the use amount of the copolymerizable non-crosslinkable and nonionic monomer exceeds 95% by weight is the same as described in the production method (I).

Such a production method (III) is preferably used when producing hollow crosslinked particles in which the amount of cationic groups and the small amount of aggregates are balanced.

<Production method (IV)> The production method (IV)
(A) When the swellable polymer particles in the production method (I) are prepared by polymerization, a cationic polymerization is carried out by using a radical polymerization initiator having a cationic group and making the swellable polymer particles cationic. A method for obtaining particles, (b) a monomer (a) using a radical polymerization initiator having a cationic group similarly to the production method (II),
(B) The method of carrying out the polymerization of (c) to make the obtained hollow crosslinked particles cationic, or (c) the method of (a) and (b) above to make the hollow crosslinked particles cationic. How to Especially, the method (c) is preferable.

The swellable polymer particles are prepared by using a radical polymerization initiator to form (b) a cationic monomer in an amount of 0 to 30% by weight, preferably 0 to 15% by weight, and more preferably 0.1 to 15% by weight.
1 to 10% by weight, and (d) 70 to 100% by weight of a nonionic monomer copolymerizable with the cationic monomer,
Preferably 85 to 100% by weight, more preferably 90%
-99.9% by weight (Total weight of monomer is 100% by weight
Is prepared by polymerizing The above (a)
In the methods (c) and (c), a radical initiator having a cationic group is used as the radical polymerization initiator, and the prepared swellable polymer particles are cationic. The swellable polymer particles comprise a monomer (a) used for polymerization,
Swellable in at least one of (b) and (c). Then, in the presence of the swellable polymer particles, as in the production method (III), (a) 1 to 100% by weight, preferably 5 to 80% by weight, more preferably 15 to 70% by weight of the crosslinkable monomer, ( b) 0 to 15% by weight of a cationic monomer, preferably 0 to 10% by weight, more preferably 0.1 to 10% by weight, and (c) 0 to 99% by weight of a copolymerizable non-crosslinkable and nonionic monomer. %,
Preferably 10 to 95% by weight, more preferably 20 to 95% by weight.
84.9% by weight (the total weight of the monomers is 100% by weight) is polymerized using a radical initiator to obtain hollow crosslinked particles. In the above methods (b) and (c), a radical initiator having a cationic group is used as the radical polymerization initiator. As described above, in the production method (IV), the radical polymerization initiator having a cationic group may be used when preparing the swellable polymer particles, and the monomers (a), (b), and (c) are polymerized. Except that a radical polymerization initiator having a cationic group may be used in this case, and the use ratio of the monomers (b) and (d) for obtaining swellable polymer particles is slightly different, the production method (II
Almost the same as I). Thus, monomers (a),
As for the polymerization method, operation, conditions and the like of (b) and (c), those described in the production method (I) are applied.

When a radical polymerization initiator having a cationic group is used for preparing the swellable polymer particles, the amount of the radical polymerization initiator used is 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the monomers (b) and (d). It is preferable to use one part by weight, more preferably 0.5 to 5 parts by weight. 0.1 used
If the amount is less than 10 parts by weight, the cationic property of the obtained hollow crosslinked particles is reduced. If the amount exceeds 10 parts by weight, the polymerization becomes unstable, which is not preferable. Monomers (a), (b),
When a radical polymerization initiator having a cationic group is used when polymerizing (c), it is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the total monomer. Department.

In preparing the above-mentioned swellable polymer particles by polymerization, a polymerization method (II
As in the case of I), the polymerization method for producing hollow crosslinked particles described in the production method (I) can be applied. In addition,
In preparation, a seed polymer may be used. When the amount of the monomer (b) used to prepare the cationic swellable polymer particles exceeds 30% by weight and is excessive (the amount of the monomer (d) is less than 70% by weight), The polymerization becomes unstable, which is not preferable.

The polymerization of the production method (IV) is carried out by the production method (II)
As in the case of I), the polymerization monomer may be only (a) a crosslinking monomer, and (b) a cationic monomer and / or
Alternatively, (c) a copolymerizable non-crosslinkable and nonionic monomer may be used in combination. (A) when the amount of the crosslinkable monomer used is less than 1% by weight, and (b) when the amount of the cationic monomer used is more than 15% by weight,
(C) Undesirable phenomena that occur when the use amount of the copolymerizable non-crosslinkable and nonionic monomer exceeds 99% by weight and the like are the same as those described in the production method (I). In the polymerization, it is preferable to use a radical polymerization initiator having a cationic group as the polymerization initiator in view of adjusting the zeta potential and stabilizing the polymerization within the scope of the present invention. In this case, the amount of the radical polymerization initiator having a cationic group is as described above.

[0055] Such a production method (IV) is characterized in that hollow crosslinked particles having extremely few aggregates can be obtained.

[Resin Component] The resin component of the resin composition of the present invention includes a thermoplastic resin and a thermosetting resin. The thermoplastic resin includes an amorphous polymer, a crystalline polymer, a liquid crystal polymer, and the like. Specifically, styrene resin, rubber reinforced styrene resin, vinyl chloride resin, acrylic resin, polyphenylene ether resin,
Examples thereof include polyarylene sulfide resin, polycarbonate resin, polyester resin, polyamide resin, polyacetal resin, polyether sulfone resin, polysulfone resin, polyimide resin, and polyolefin resin.

Styrene resins useful in the present invention include:
Polystyrene, polychlorostyrene, poly-α-methylstyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-α-methylstyrene copolymer, styrene-α -Methylstyrene-methyl methacrylate copolymer, styrene-α-methylstyrene-acrylonitrile-methyl methacrylate copolymer, and the like. These can be used alone or in combination of two or more. Examples of the rubber-reinforced styrenic resin useful in the present invention include high-impact polystyrene, ABS resin, AES resin, AAS resin, MBS resin, and the above-mentioned high-impact polystyrene, ABS
Resins using styrene-butadiene block copolymers or hydrogenated products of the copolymers in place of butadiene rubber which is a rubber component of resins and MBS resins.
These can be used alone or in combination of two or more. Further, it can be used in combination with the styrene resin.

The vinyl chloride resins useful in the present invention include polyvinyl chloride, vinyl chloride, and 50% by weight or less.
Preferably, a copolymer of 45% by weight or less of vinyl chloride and a compound having at least one double bond copolymerizable with vinyl chloride can be exemplified. Specific examples of the compound having at least one copolymerizable double bond include vinylidene chloride, ethylene, propylene, vinyl acetate, (meth) acrylic acid and their esters, maleic acid and their esters, and acrylonitrile. Can be mentioned. The polymerization degree of the vinyl chloride resin is usually 400 to
4500, and particularly preferably 400 to 1500.

The polyarylene sulfide resin useful in the present invention contains at least 70 mol% of a structural unit represented by the formula:-(Ar-S)-. Where Ar
Is p-phenylene, m-phenylene, 2,6-naphthalene, 4,4′-biphenylene, p, p′-bibenzyl,
And an aromatic group having 6 or more carbon atoms, such as a substituted product thereof. Among them, the unsubstituted p-phenylene nucleus, that is, the following formula:

[0060]

Embedded image

Poly-p- having a structural unit represented by
Phenylene sulfide is preferred from the viewpoint of moldability.

Examples of useful polycarbonate resins in the present invention include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aliphatic-aromatic polycarbonate resins. Generally, 2,2-bis (4
A polymer or copolymer obtained by polymerizing bisphenols such as-(oxyphenyl) alkane, bis (4-oxyphenyl) ether, bis (4-oxyphenyl) sulfone sulfide or sulfoxide, which is required Is a polymer using bisphenols substituted by halogen according to

As a typical example of the polyester resin useful in the present invention, poly (ethylene terephthalate) (PE
T), polyester resins obtained from aromatic dicarboxylic acids and dihydric alcohols such as poly (propylene terephthalate), poly (butylene terephthalate) (PBT), poly (pentamethylene terephthalate) and poly (hexamethylene terephthalate). Can be Moreover,
A so-called polyarylate resin, which is an aromatic polyester resin obtained from an aromatic dicarboxylic acid and an aromatic diphenol, can be mentioned. Specific examples of the polyarylate resin include a polyester resin and a copolyester resin of bisphenol A and terephthalate acid or isophthalic acid. Of these, PET and PBT are particularly preferred.

The polyamide resin useful in the present invention has the formula: H
(Wherein, x is a is 3-12 _{integer) 2 N- (CH 2) x} -NH 2 and the linear Ajimin represented by the formula: HOOC-
(CH ₂ ) y —COOH (where y is an integer of 2 to 12) and those produced by condensation with a linear dicarboxylic acid and those produced by ring-opening polymerization of lactams. be able to. Preferred examples of these polyamide resins include Niro 6,6, Nylon 6,10, Nylon 6,12, Nylon 4,6, Nylon 3,4, Nylon 6,9, Nylon 6, Nylon 1.
2, nylon 11, nylon 4, and the like. In addition, nylon 6 / 6,10, nylon 6 / 6,12, nylon 6
/ 4,6, nylon 6/12, nylon 6 / 6,6, nylon 6 / 6,6 / 6,10, nylon 6 / 4,6 /
6,6, nylon 6 / 6,6 / 6,12, nylon 6 /
Copolymer polyamides such as 4, 6/10 and nylon 6/4, 6/12 are also preferred. In addition, nylon 6/6
T (T: terephthalic acid component), a semi-aromatic polyamide resin obtained from an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and meta-xylylenediamine or an alicyclic diamine, meta-xylylenediamine and the above-mentioned linear dicarboxylic acid And polyamide resin, polyester amide resin, polyether amide resin, polyester ether amide resin and the like.

Examples of the polyolefin resin include polyethylene, polypropylene and the like.

Examples of the thermosetting resin as the resin component of the present invention include a phenol resin, an epoxy resin, a melamine resin, an unsaturated polyester resin, an alkyd resin and the like. Resins and unsaturated polyester resins are preferred, and phenol resins and epoxy resins are more preferred.

In the resin composition of the present invention, the ratio of the resin component to the cationic hollow crosslinked polymer particles is preferably 30 to 99.9% by weight, more preferably 5 to 99.9% by weight.
0 to 99.9% by weight, particularly preferably 50 to 99.5% by weight, and the cationic hollow crosslinked polymer particles are preferably 70 to 0.1% by weight, more preferably 50 to 0.1% by weight.
% By weight, particularly preferably 50 to 0.5% by weight (where the total amount of both is 100% by weight). If the proportion of the cationic hollow crosslinked polymer particles is less than 0.1% by weight, the effect of adding the particles cannot be obtained, while if it exceeds 70% by weight, the performance of the resin component is undesirably reduced.

The method of mixing the thermoplastic resin, which is a resin component of the composition of the present invention, with the cationic hollow crosslinked polymer particles may be, for example, a powder of a thermoplastic resin, or a pellet and a powder of the cationic hollow crosslinked polymer particles. Blend the thermoplastic resin latex and the latex of the cationic hollow cross-linked polymer particles obtained by the method of directly mixing the polymer or the emulsion polymerization method, then co-coagulate, recover the polymer component, and dry the resin. A resin composition using a thermoplastic resin as a component can be obtained. The method using the latex blend is a method suitable for a thermoplastic resin obtained by an emulsion polymerization method, for example, when a rubber-reinforced styrene resin such as an ABS resin is used.

In addition, the above resin composition may be a known antioxidant such as 2,6-di-tret-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,
6-dimethylphenol, 2,2'-methylene-bis (4
-Ethyl-6-tert-butylphenol), 4,4 '
-Thiobis- (6-tert-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, wax; known UV absorbers such as p-tert-butylphenyl salicylate; 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzothiazole; known lubricants such as silicone oil paraffin wax, stearic acid, hardened oil, stearamide, Methylene bis stearoamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; known flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, tricresyl phosphate, chlorinated Raffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; known antistatic agents, such as stearoamidopropyldimethyl-β-hydroxyethylammonium nitrate; known colorants, such as titanium oxide, carbon black, and others. Inorganic or organic pigments; known fillers,
For example, calcium carbonate, clay, silica, glass fiber,
Glass spheres, carbon fibers, and the like can be added as needed.

A preferred method of mixing the thermosetting resin and the cationic hollow crosslinked polymer particles is a method of heating and mixing. For mixing, a closed mixer such as a Banbury mixer, a roll, an extruder, or the like can be used according to the purpose.
In addition, the composition in which the resin component is a thermosetting resin, if necessary, an antioxidant or an antioxidant, a softener, various inorganic or organic fillers, a reinforcing agent, a crosslinking agent, Glass fibers, metal fibers, carbon fibers and the like can be blended. A composition using a thermosetting resin can be obtained by a molding method described in “Introduction to Plastics (issued by the Industrial Research Institute), pp. 80, 81”, such as a hand lay-up method, a spray-up method, a FW method, SMC method, continuous drawing method, BMC method,
A desired molded product can be obtained by using a premix method, a preform method, an FRP method, or the like.

The resin composition of the present invention containing a thermoplastic resin as a resin component is used as a molding material for various molded articles known per se, depending on the type of the thermoplastic resin. on the other hand,
The resin composition of the present invention containing a thermosetting resin as a resin component,
It can be widely used in applications known per se, for example, coating materials, casting materials, molding materials, adhesives, paints, etc. mainly for electric / electronic parts, automobiles, and building materials.

[0072]

EXAMPLES The present invention will be described below in detail with reference to examples, but the scope of the present invention is not limited by the examples. In the following description,
“Parts” and “%” are based on weight.

Synthesis Example 1 <Synthesis of Cationic Hollow Cross-Linked Polymer Particles (A)> (Preparation of Seed Particle A) In a temperature-controlled autoclave equipped with a stirrer, 600 parts of water, 27% of dodecyltrimethylammonium chloride 5 parts of solution (Coatamine 24P manufactured by Kao Corporation), 1 part of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50 manufactured by Wako Pure Chemical Industries, Ltd.), 75 parts of styrene, acrylonitrile 10 parts, 2-ethylhexyl acrylate 10
Parts, 5 parts of methylene chloride quaternary salt of dimethylaminopropylacrylamide and 15 parts of t-dodecylmercaptan were charged all at once, reacted at 70 ° C. for 3 hours, cooled, and cooled.
The mixture was filtered through a 00 mesh wire net to obtain seed particles A as swellable polymer particles.

(Production of Hollow Crosslinked Particles by Polymerization) 430 parts of water 10 parts of seed particles A (solid content) 2,2′-azobis (2-methylpropionamidine) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) V-50) 1 part Methyl methacrylate 59 parts Styrene 12 parts Divinylbenzene 28 parts were charged all at once, reacted at 70 ° C. for 3 hours, cooled, and cooled.
Filtration through a 300-mesh wire net removed coarse particles to obtain an aqueous dispersion containing the cationic hollow crosslinked polymer particles (A). About this cationic hollow crosslinked polymer particle,
The zeta potential, the volume hollow ratio, and the average particle size were measured by the methods described above. In addition, as a zeta potential measuring device, BROOK
A dynamic light scattering method for measuring an average particle diameter using "Zetaplus" manufactured by HAVENINSTRUMENTS, and using "JEM-100SX" manufactured by JEOL Ltd. as a transmission electron microscope for measuring volumetric porosity. "LPA-3000 / 3" manufactured by Otsuka Electronics Co., Ltd.
100 "was used.

(Measurement results) Zeta potential: +40 mV at pH2, +36 m at pH6
V, +32 mV at pH 9, Volume hollow ratio; 30% Average particle diameter; 0.2 μm

The aqueous dispersion containing the cationic hollow crosslinked polymer particles (A) was dried using a spray drier to obtain a powder of the cationic hollow crosslinked polymer particles (A).

Synthesis Example 2 <Synthesis of anionic hollow crosslinked polymer particles (B)> 70 parts of styrene, 27 parts of butadiene, 3 parts of itaconic acid and 12 parts of t-dodecyl mercaptan, 200 parts of water and 0.2 part of sodium lauryl sulfate. While stirring an aqueous solution in which 5 parts and 1.0 part of potassium persulfate were dissolved, polymerization was carried out at 70 ° C. for 8 hours to obtain polymer particles. The polymer particles had an average particle size of 0.24 μm, a toluene-insoluble content of 6%, and a number average molecular weight of 5.0 by GPC.
00, the ratio of the weight average molecular weight to the number average molecular weight (Mw / M
n) was 2.6. Next, the polymer particles are used as seed particles, and the polymer particles are
Parts, polyoxyethylene nonyl phenyl ether 0.1
, 0.4 part of sodium lauryl sulfate and 0.5 part of potassium persulfate were dispersed in 900 parts of water. 30 parts of methyl methacrylate, 50 parts of divinylbenzene, 18 parts of α-methylstyrene, 2 parts of acrylic acid and 2 parts of toluene
When 0 parts of the mixture was added and polymerized at 70 ° C. for 5 hours,
A dispersion of capsule particles containing toluene inside the particles was obtained with a polymerization yield of 98%. After this dispersion was subjected to a steam strip treatment, the polymer particles were observed with a transmission electron microscope. The polymer particles were transparent at the center and were completely spherical anionic hollow crosslinked polymer particles. Was. The outer diameter of the particles was 0.44 μm and the inner diameter was 0.3 μm. Zeta potential: -5 mV at pH 2, -28 mV at pH 6,
-35 mV at pH 9 Volume hollow ratio: 30% Average particle diameter: 0.44 μm

The aqueous dispersion containing the anionic hollow crosslinked polymer particles (B) was dried using a spray dryer to obtain a powder of the anionic hollow crosslinked polymer particles (B).

Examples 1 to 8 and Comparative Examples 1 to 8 The thermoplastic resin pellets shown in Tables 1 and 2 and the cationic hollow crosslinked polymer particles (A) shown in Table 1 or the anionic hollow particles shown in Table 2 The crosslinked polymer particles (B) were mixed using a Henschel mixer (this mixing method is called a dry method). Thereafter, the mixture was supplied to an extruder, melt-mixed, and a plate was extruded. A test piece for measuring Izod impact strength was cut out from this plate, and subjected to ASTM D-256.
The Izod impact strength was measured according to (notched). The measurement results are shown in Table 1 (Examples 1 to 8) and Table 2 (Comparative Examples 1 to 8).

T1 to T6 shown in Tables 1 and 2 are the following resins. T-1: an ABS resin having a polybutadiene rubber content of 20%, a styrene monomer unit content of 60%, an acrylonitrile monomer unit content of 20%, and a graft ratio of 35% -2: an ABS resin having a polybutadiene rubber content of 40%, a styrene monomer unit content of 45%, an acrylonitrile monomer unit content of 15%, and a graft ratio of 50%. 3: Copolymer of 75% styrene and 25% acrylonitrile T-4: Polycarbonate resin T-5: Polybutylene terephthalate resin T-6: Nylon 6 resin

[0081]

[Table 1]

[0082]

[Table 2]

Example 9 Using the cationic hollow crosslinked polymer particles (A), a thermosetting resin composition (epoxy resin composition) was obtained according to the following procedure. Cresol novolak type epoxy resin (epoxy equivalent 200) 100 parts by weight Phenol resin (novolak type) 50 parts by weight Curing agent (2-methylimidazole) 5 parts by weight Cationic hollow crosslinked polymer particles (A) 37.5 parts by weight Using a closed mixer, knead sufficiently at about 80 ° C, perform brass forming at 160 ° C, process the formed plate with a milling machine to prepare a sample for evaluating physical properties, and prepare ASTM D-256 (notched). ) According to Izod impact strength and according to ASTM D-790. Table 3 shows the measurement results.

Examples 10 and 11 and Comparative Examples 9 to 11 The same procedure as in Example 9 was carried out except that the components shown in Table 3 were used. Table 3 shows the evaluation results.

[0085]

[Table 3]

The following is clear from the results shown in Tables 1 and 2. In the case of the examples using the cationic hollow crosslinked polymer particles, the impact resistance is superior to that of the comparative example using the conventional anionic hollow crosslinked polymer particles. This is because the resin composition of the example of the present invention has a stronger affinity between the hollow particles and the thermoplastic resin as the matrix. Further, from the results shown in Table 3, the same can be said for the composition using the thermosetting resin.

[0087]

According to the resin composition of the present invention, a cationic hollow cross-linked polymer particle is generally blended with an anionic resin material. A high-rigidity, whitened or opaque molded product can be obtained without impairing the inherent lightness, excellent mechanical properties and optical properties (surface gloss and color tone) inherent in. In addition, the cationic hollow crosslinked polymer particles blended in the resin composition of the present invention maintain cationicity in a wide pH range, so that a molded article of the resin composition of the present invention becomes cationic and a molded article In addition to being excellent in secondary workability such as good coating on the surface, it can impart antistatic properties to the molded product surface for a long period of time.

 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4J002 AA01W AC02X BB10X BB28X BC06W BC10X BD05X BD12X BG07X BN15W CC07X CD13X CF07W CF13X CG00W CG02X CK02X CL01W 4J011 PA63 PA65 PA66 PA69 PA85 PA95 PC88 PA89

Claims (3)

[Claims] 1. A resin composition comprising a resin and cationic hollow crosslinked polymer particles having a zeta potential measured in an aqueous medium having a pH of 2 to 9 in a range of +5 to +100 mV. 2. The cationic hollow crosslinked polymer particles have 5 to 90% by weight of a structural unit derived from a crosslinkable monomer and 95 to 10% by weight of a structural unit derived from another monomer copolymerizable with the crosslinkable monomer. (Where the total amount of both is 1
2. The resin composition according to claim 1, wherein 3. The cationic hollow crosslinked polymer particle according to claim 1,
(1) Using a radical polymerization initiator, (a) 1 to 100% by weight of a crosslinkable monomer, and (b) cationic monomer 0 to 1
5% by weight, and (c) 0-99% by weight of the copolymerizable non-crosslinkable and nonionic monomers (total weight of monomers is 100% by weight), swelling with respect to at least one of these monomers Produced by polymerizing in the presence of possible polymer particles, and (2) the polymer particles are prepared by using a radical polymerization initiator to form (b) 0 to 30% by weight of a cationic monomer and (d) )
Polymer particles obtained by polymerizing 70 to 100% by weight of a nonionic monomer copolymerizable with the cationic monomer (the total amount of the monomers is 100% by weight);
3. The resin composition according to claim 1, wherein (3) one or both of the radical polymerization initiators in (1) and (2) are radical initiators having a cationic group.